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# Ultrafast collective dynamics of short-range charge/orbital ordering fluctuations in colossal magnetoresistive oxides

## Abstract

The “colossal magnetoresistive” (CMR) manganites are highly correlated systems with a strong coupling between spin, charge, orbital, and lattice degrees of freedom, which leads to complex phase diagrams and to the coexistence of various forms of ordering. For example, nanoscale charge/orbital ordering (CO) fluctuations appear to cooperate with Jahn-Teller (JT) distortions of the MnO6 octahedra in CMR manganites and compete with the electron itinerancy favored by double exchange. However, access to the ordered dynamical state has been challenging, mostly due to intrinsic experimental difficulties in measuring fast short-range correlations. Here, we report on a strongly damped low-energy collective mode originating from fast short-range CO fluctuations in La0.67Ca0.33MnO3 (LCMO) single crystal and thin films. We elucidate the collective mode in terms of its dispersion relation and dependence on average A-site ion radius, rA, and hole-doping concentration. Our results show for the first time that dynamical short-range CO correlations in CMR manganites can be detected with high momentum resolution by coherent ultrafast optical techniques.

Charge/orbital ordering (CO) is a common characteristic of transition metal oxides with perovskite structure . Recent neutron scattering experiments showed that fast short-range correlation of the so-called CE-type charge ordering exists in the colossal magneto-resistive (CMR) manganite, LCMO, above the Curie temperature, $`T_C`$ . The coupled dynamics of fluctuating CO phases and Jahn-Teller (JT) distortions of the MnO6 octahedra are found to be crucial for the metal-insulator (MI) phase transition and the CMR effect . Therefore, it is fundamentally important to elucidate the dynamics of short-range charge/orbital stripes in CMR materials.

Ultrafast optical techniques have provided significant insight into coupled electron, lattice and spin dynamics in metals , and more recently, transition metal oxides . In this work, we investigate for the first time the collective dynamics of short-range CO fluctuations in CMR manganites by time-resolved optical spectroscopy. The period of the CO modulations show strong dependence on hole doping concentration and average A-site ion radius, which is explained by different correlation length and strength in these materials. We obtain a coherence length of $``$250 nm for LCMO and $`>>`$2.5 $`\mu `$m for LaMnO3 (LMO). The overdamped behavior in LCMO is due to inhomogeneous dephasing, whereas in LMO, the damping rate is very small because of the static and long-range correlation. Our results show that the time-resolved optical technique provides momentum-resolved spectroscopic information on the low-energy dynamics of short-range CO fluctuations in colossal magneto-resistive materials. This important new information is relevant for elucidation of collective transport phenomena in strongly correlated electron systems.

In the time-resolved optical experiments, the change of reflectivity ($`\mathrm{\Delta }R`$) induced by the pump beam is measured as a function of time delay for different wavelengths of the probe beam ($`\lambda _{probe}=400`$ nm - 2.5 $`\mu `$m) in both LCMO single crystal and thin films. Figure 1 shows typical time evolution of $`\mathrm{\Delta }R`$ for LCMO thin film and LMO single crystal as a function of time delay $`\mathrm{\Delta }t`$ between the pump and probe pulses. The data are taken at 285 K and 35 K with pump and probe wavelength of 800 nm, respectively. After the initial laser pulse excitation, the decay of $`\mathrm{\Delta }R`$ clearly shows an oscillatory component on top of a multi-exponential decay.

Here, we discuss only the slow oscillatory component observed in the trace of $`\mathrm{\Delta }R`$ from LCMO and LMO (Fig. 1). Figure 2 displays the coherent overdamped oscillations of $`\mathrm{\Delta }R`$ from LCMO thin film without the exponentially decaying part as a function of probe wavelength in the range 400 nm to 2300 nm. The oscillations are heavily damped and strongly dispersive. Only one, at most two oscillations, are observed in the whole wavelength range. The frequency of the oscillations decreases from 73.83 GHz at 400 nm to 21.8 GHz at 2300 nm.

Figure 3 shows the dispersion relation of the slow oscillation of $`\mathrm{\Delta }R`$ from LCMO thin film at 285 K. The wave number is given by $`q=2n/\lambda `$, where $`\lambda `$ is the probe wavelength and $`n`$ is the refractive index of LCMO . The frequency of the coherent oscillations increases proportional to the wave number of the excited mode. The slope gives a phase velocity for the collective mode of $`c_\varphi =`$ $`7.1\pm 0.3\times 10^3`$ m/s along the $`c`$-axis.

The coherent oscillations of $`\mathrm{\Delta }R`$ show strong dependence on hole doping concentration and average A-site ion radius, $`r_A`$. The former is clearly revealed in $`\mathrm{\Delta }R`$ from LMO (Fig. 1). Similar to the LCMO sample, $`\mathrm{\Delta }R`$ also exhibits a slow oscillatory component on top of a bi-exponential decay in the parent compound LMO. However, the 800-nm data from LMO reveal a different modulation period of $``$ 45 ps, in contrast to $``$ 27.6 ps observed in LCMO (Fig. 1). The oscillations also show a strong dependence on A-site substitution (average A-site ion radius, $`r_A`$). The modulation period for PCMO single crystal at 800 nm is $``$ 40 ps , which is much longer than in LCMO.

These observations strongly suggest that the coherent oscillations originate from a low-energy collective mode in LCMO. The fact that the period of the oscillations is longer in the parent compound LMO and PCMO, which has a smaller average ionic radius than LCMO, can be explained by different correlation length and strength in these materials. As compared to LCMO, where the charge/orbital correlations are short-range in nature due to the presence of ferromagnetic phases, the charge/orbital coupling is stronger and long-range in both LMO and the smaller bandwidth manganite PCMO. The case of LMO, with no double-exchange carriers, is a typical example in which the orbital ordering is enhanced by the increase of Jahn-Teller interaction. The stronger charge/orbital correlation in LMO results in a heavier effective mass than in LCMO. The phase velocity of the collective modes is determined by the effective mass and the Fermi velocity, $`v_F`$ :

$`c_\varphi =({\displaystyle \frac{m}{m^{}}})^{1/2}v_F`$

which is therefore smaller in LMO than in LCMO. We expect a longer oscillation period in LMO since the modulation period is inversely proportional to the phase velocity of the material. Similarly, the ground state of PCMO exhibits charge-localizing real space ordering of Mn3+ and Mn4+ ions that occurs at $``$220 K. The charge/orbital correlation in PCMO is enhanced by the increase of orthorhombic distortion of GdFeO3-type . Thus, a longer oscillation period is expected in PCMO as well.

Another particularly intriguing result is the strong doping concentration dependence of the damping rate of the coherent oscillations in LCMO. As shown in Fig. 1, the coherent oscillations in LMO persist for at least 600 ps ($``$15 periods) with very little damping whereas at most two periods of the collective mode can be observed in LCMO. Since the optical properties of LCMO and LMO are very similar at photon energies in the near infrared to visible range , the stronger damping observed in LCMO must be directly related to the damping of the collective mode. The results shown in Fig. 1 allow us to extract the coherence length

$`\lambda =\tau c_\varphi `$

for LCMO and LMO, which depends essentially on the damping time $`\tau `$ of the collective mode. We obtain a coherence length of $``$250 nm for LCMO and $`>>`$2.5 $`\mu `$m for LMO. The overdamped behavior in LCMO may result from inhomogeneous spatial distribution (inhomogeneous dephasing) and the dynamical nature of the short-range charge/orbital ordering phases. The coherence length for LCMO is of the same order of magnitude as the charge/orbital correlation length of the CE-type phase in perovskite manganites with a characteristic length scale of stripe domains on the order of 100 lattice spacings . In contrast, the damping rate is very small for LMO, because the orbital domains in LMO are static and the correlation is long-range. There is also a very limited phase space available for scattering into other modes in the wavelength range investigated.

The inset of Fig. 1 illustrates the optically excited collective modes in LCMO and LMO. The photo-generated charge/orbital ordering modulations cause complex rotations of the MnO6 octahedra, which oscillate along the modulation direction. The collective modes propagate from the surface in the crystallographic c-direction and approach zero with increasing distance from the origin due to the finite range of correlations.

Finally, we present a simple physical model that accounts correctly for the excitation and detection of the coherent charge/orbital-ordering oscillations. The number of photons per pulse and unit volume absorbed in the sample is $``$1020 photons/cm3, comparable to the charge-carrier density ($``$1020-10$`^{21\text{ }}`$holes/cm3) in LCMO; hence, one expects significant electron excitation during ultrashort pump pulse illumination. This can lead to coherent excitation of collective modes . We use a tunable optical probe pulse to detect the various frequency components of the photo-generated collective modes. In the back-scattering geometry (Fig. 4), part of the probe pulse is reflected by the wave front of the excited collective modes and the remainder at the surface of the sample. These reflections interfere constructively or destructively depending on the position and time of the charge density modulation. Further, the momentum selection rule for back scattering is $`q_i+q_f=q\mathrm{cos}\theta `$, where $`q_i`$ and$`q_f`$ are the wave vectors of the incident and scattered probe beam in the material, and $`\theta `$ is the probe beam incident angle ($`\theta 0^{}`$). Therefore, for a given probe wavelength phase-matching occurs exclusively for a single collective mode wavevector. This process causes the probe signal to oscillate with time delay relative to the pump pulse. The new scheme provides momentum-resolved spectroscopic information of collective modes in solids.

In summary, we investigated fast short-range CO fluctuations in LCMO by time-resolved optical spectroscopy. The amplitude, period and damping of the CO modulations show strong dependence on hole doping and average A-site ion radius. The results reported here have great significance for understanding the competition/cooperation behavior and nanoscale phase separation in colossal magnetoresistive manganites. Our scheme represents a new approach to investigate low-energy collective dynamics in strongly correlated electron systems with high-momentum resolution.

Methods

LCMO and LMO single crystals and thin films were grown by the floating zone method and pulsed laser deposition. The samples were characterized by electrical resistivity and magnetization measurements. The LCMO single crystal and 400-nm thin film (grown on NdGaO3 (110) substrate) have a Curie temperature $`T_C`$ = 225 K and 260 K, respectively. The LMO single crystal shows a Neel temperature $`T_N`$ = 145 K. For the transient reflectivity measurements the samples were mounted in an optical cryostat. The laser system consists of a Ti:sapphire regenerative amplifier (Spitfire, Spectra-Physics) and an optical parametric amplifier (OPA-800C, Spectra-Physics) delivering 100-fs short pulses at a 1-kHz repetition rate tunable from 600 nm to 10 $`\mu `$m. A two-color pump-probe setup is employed with the pump beam power $`<`$ 6 mW and the probe beam power $`<`$ 1 mW. The unfocused pump beam, spot-diameter $``$2 mm, and the time-delayed probe beam are overlapped on the sample with their polarization perpendicular to each other. The reflected probe beam is detected with a photodiode detector. A SR250 gated integrator & boxcar averager, and a lock-in amplifier are used to measure the transient reflectivity change $`\mathrm{\Delta }R`$ of the probe beam.

Current address for C. S. Hong, Department of Chemistry, Korea university, Anam-dong, Sungbuk-ku, Seoul 136-701, Republic of Korea

Acknowledgements

This work is supported in part by NSF through grants: DMR-0137322, IMR-0114124 (CWM), and DMR-9876266 (PSU), and the Petroleum Research Fund (PSU).

Correspondence and requests for materials should be addressed to G. L.

Competing financial interests

The authors declare that they have no competing financial interests.

Figure captions

Figure 1. Time evolution of reflectivity change, $`\mathrm{\Delta }R`$, for LCMO thin film at 285 K and LMO single crystal at 35 K. The transient reflectivity clearly reveals coherent oscillations on top of a multi-exponential decay. The inset shows a schematic illustration of optically excited collective modes in LCMO and LMO. The photo-generated charge/orbital ordering modulations cause complex rotations of the MnO6 octahedra, which oscillate along the modulation direction and approach zero with increasing distance from the origin due to the finite range of correlations.

Figure 2. a) Time evolution of $`\mathrm{\Delta }R`$ from LCMO thin film for probe wavelengths from ultraviolet (400 nm) to mid-infrared (2300 nm); b) Fourier transforms of $`\mathrm{\Delta }R`$ traces shown in a).

Figure 3. Collective mode dispersion relation of LCMO thin film with thickness 400 nm grown on NdGaO3 (110) substrate at 285 K. Solid squares: the experimental data. Solid line: the predicted dependence $`\nu =2nc_\varphi \mathrm{cos}\theta /\lambda `$, with $`\lambda `$ the probe wavelength, $`n`$ the refractive index of LCMO, and $`\theta `$ the probe beam incident angle ($`\theta 0^{}`$).

Figure 4. Schematic of photo-induced coherent CO mode excitation and detection mechanism. The strong absorption of ultrashort pump pulses generates broad-band coherent CO oscillations. The modes propagate into the sample and are detected in the back-scattering geometry by tunable optical probe pulses. Momentum selection rule for back scattering is $`q_i+q_f=q\mathrm{cos}\theta `$, with $`q_i`$ and$`q_f`$ the wave vectors of the incident and scattered probe beam in the material.


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# Measurement of Non-Random Event-by-Event Fluctuations of Average Transverse Momentum in √𝑠_{𝑁𝑁}=200 GeV Au+Au and p+p Collisions

PHENIX Collaboration

## Abstract

Event-by-event fluctuations of the average transverse momentum of produced particles near mid-rapidity have been measured by the PHENIX Collaboration in $`\sqrt{s_{NN}}=200`$ GeV Au+Au and p+p collisions at the Relativistic Heavy Ion Collider. The fluctuations are observed to be in excess of the expectation for statistically independent particle emission for all centralities. The excess fluctuations exhibit a dependence on both the centrality of the collision and on the $`p_T`$ range over which the average is calculated. Both the centrality and $`p_T`$ dependence can be well reproduced by a simulation of random particle production with the addition of contributions from hard scattering processes.

The measurement of fluctuations in the event-by-event average transverse momentum of produced particles in relativistic heavy ion collisions has been proposed as a probe of phase instabilities near the QCD phase transition Heis01 ; Step98 ; Step99 , which could result in classes of events with different properties, such as the effective temperature of the collision. Fluctuation measurements could also provide information about the onset of thermalization in the system Gav03 . The resulting phenomena can be observed by measuring deviations of the event-by-event average $`p_T`$, referred to here as $`M_{p_T}`$, of produced charged particles from the expectation for statistically independent particle emission Stod95 ; Shur98  after subtracting contributions from fluctuations arising from physical processes such as elliptic flow and jet production.

Several $`M_{p_T}`$ fluctuation measurements have been reported in heavy ion collisions NA49 ; CERES ; PPG005 ; STAR , including a study by PHENIX PPG005  in $`\sqrt{s_{NN}}=130`$ GeV Au+Au collisions which set limits on the magnitude of non-random fluctuations in $`M_{p_T}`$. Recently, STAR has reported fluctuations in excess of the random expectation, within the PHENIX limits, at the same collision energy STAR . For the first results from $`\sqrt{s_{NN}}=200`$ GeV Au+Au and p+p collisions reported here, upgrades of the PHENIX central arm spectrometers PHNIM  have expanded the azimuthal acceptance from $`58.5^{}`$ to $`180.0^{}`$ within the pseudorapidity range of $`|\eta |<0.35`$. Pad chamber and calorimeter detectors have also been utilized for improved background rejection. As a result, the sensitivity of the PHENIX spectrometer to the observation of fluctuations in $`M_{p_T}`$ due to event-by-event fluctuations in the effective temperature PPG005 ; Korus01  has improved by greater than a factor of two.

Minimum bias events triggered by a coincidence between the Zero Degree Calorimeters (ZDC) and the Beam-Beam Counters (BBC), with a requirement that the collision vertex, which is measured with an r.m.s. resolution of less than 6 mm in central collisions and 8 mm in the most peripheral collisions, be within 5 cm of the nominal origin, are used in this analysis. Event centrality for Au+Au collisions, which is defined using correlations in the BBC and ZDC analog response PPG002 , is divided into several classes, each containing an average of 244,000 analyzed events. These classes are associated to the estimated average number of participants in the collision, $`<N_{part}>`$, which is derived using a Glauber model Monte Carlo calculation with the BBC and ZDC detector response taken into account Glauber .

Charged particle momenta are reconstructed in the PHENIX central arm spectrometers with a drift chamber and a radially adjacent pixel pad chamber. Non-vertex track background rejection is provided by pixel pad chambers and calorimeters located further outward radially from the collision vertex Mit02 . The momentum resolution is $`\frac{\delta p}{p}0.7\%1.0\%\times p`$ (GeV/c).

$`M_{p_T}`$ is calculated for each event, which contains a number of reconstructed tracks within a specified $`p_T`$ range, $`N_{tracks}`$. The $`p_T`$ range is always given a lower bound of 200 MeV/c and a varying upper bound, $`p_T^{max}`$, from 500 MeV/c to 2.0 GeV/c. There is a minimum $`N_{tracks}`$ cut of 3 in both Au+Au events (removing 0%, 4.6%, and 29% of events in the 0-50%, 50-60%, and 60-70% centrality ranges, respectively, when $`p_T^{max}`$ = 2.0 GeV/c) and p+p events (removing 59% of the events).

There are several measures by which the magnitude of non-random fluctuations can be quantified, namely $`\varphi _{p_T}`$ Gaz92 ; Mro98 , $`\nu _{dynamic}`$ Pru02 , and $`F_{p_T}`$ PPG005 . The calculation of $`F_{p_T}`$ is based upon the magnitude of the fluctuation, $`\omega _{p_T}`$, defined as

$$\omega _{p_T}=\frac{(<M_{p_T}^2><M_{p_T}>^2)^{1/2}}{<M_{p_T}>}=\frac{\sigma _{M_{p_T}}}{<M_{p_T}>}.$$
(1)
$`F_{p_T}`$ is defined as the fractional deviation of $`\omega _{p_T}`$ from a baseline estimate defined using mixed events,

$$F_{p_T}=\frac{(\omega _{(p_T,data)}\omega _{(p_T,mixed)})}{\omega _{(p_T,mixed)}}.$$
(2)
Mixed event $`M_{p_T}`$ distributions are validated by comparisons to a calculation of $`M_{p_T}`$ assuming statistically independent particle emission using parameters extracted from the inclusive $`p_T`$ distributions of the data Tan01 . For the 0-5% centrality class, which suffers the most from tracking inefficiency, the effects of two-track resolution, and background contributions, the mixed event $`M_{p_T}`$ distribution yields a value of $`F_{p_T}=0.04\%`$ with respect to the calculation. The results of this comparison are included in the estimates of the systematic errors. Further details on the mixed event procedure and a discussion of contributions to the value of $`F_{p_T}`$ from detector efficiency and resolution effects can be found in the description of the data analysis of $`\sqrt{s_{NN}}=130`$ GeV Au+Au collisions PPG005 .

Comparisons of the data and mixed event $`M_{p_T}`$ distributions for the 0-5% and 30-35% centrality classes are shown in Fig. 1. Any excess fluctuations are small and are difficult to distinguish by eye in a direct overlay of the $`M_{p_T}`$ distributions. Therefore, the comparison is also shown as residuals of the difference between the data and mixed event distributions in units of standard deviations of the individual data points. The double-peaked shape in the residual distributions is an artifact of the fact that the mixed event distributions, which always have a smaller standard deviation in $`M_{p_T}`$ than the data, are normalized to minimize the total $`\chi ^2`$ of the residual distribution.

Figure 2 shows the magnitude of $`F_{p_T}`$, expressed in percent, as a function of centrality for Au+Au collisions with $`p_T^{max}`$ = 2.0 GeV/c. The error bars are dominated by time-dependent systematic effects during the data taking period due to detector variations, which are minimized using strict time-dependent cuts on the mean and standard deviations of the inclusive $`p_T`$ and $`N_{tracks}`$ distributions. Statistical errors are below $`F_{p_T}`$ = 0.05% for all centralities. The systematic errors are determined by dividing the entire dataset into ten separate subsets for each centrality class and extracting the standard deviation of the $`F_{p_T}`$ values calculated for each subset. From Fig. 2, a significant non-random fluctuation is seen that appears to peak in mid-central collisions. However, the magnitude of the observed fluctuations are within previously published limits PPG005 . In addition, the value of $`F_{p_T}`$ for the most peripheral Au+Au collisions is consistent with, albeit slightly below, the value measured by the same PHENIX apparatus in minimum bias $`\sqrt{s_{NN}}`$ = 200 GeV p+p collisions. If the magnitude of $`F_{p_T}`$ is entirely due to fluctuations in the effective temperature of the system Korus01 , this measurement corresponds to a fluctuation of $`\sigma _T/<T>`$=1.8% at 0-5% centrality and 3.7% at 20-25% centrality.

To further understand the source of the non-random fluctuations, $`F_{p_T}`$ is measured over a varying $`p_T`$ range for which $`M_{p_T}`$ is calculated, $`0.2`$ GeV/c $`<p_T<p_T^{max}`$. Figure 3 shows $`F_{p_T}`$ plotted as a function of $`p_T^{max}`$ for the 20-25% centrality class. A trend of increasing $`F_{p_T}`$ for increasing $`p_T^{max}`$ is observed for this and all other centrality classes. The majority of the contribution to $`F_{p_T}`$ appears to be due to correlations of particles with $`p_T>1.0`$ GeV/c, where $`F_{p_T}`$ increases disproportionately to the small increase (only 14%) of $`N_{tracks}`$ in this region.

The behavior of $`F_{p_T}`$ as a function of centrality and $`p_T`$ is similar to trends seen in measurements of elliptic flow phenixFlow . The contribution of elliptic flow to the magnitude of $`F_{p_T}`$ is investigated using a Monte Carlo simulation whereby events are generated with a Gaussian distribution of $`N_{tracks}`$ particles determined by a fit to the data and a random reaction plane azimuthal angle, $`\mathrm{\Phi }`$, between 0 and $`2\pi `$. Independent particles within an event are generated following the inclusive $`p_T`$ distribution with azimuthal angles, $`\varphi `$, distributed according to collective elliptic flow described by the function $`\frac{dN}{d(\varphi \mathrm{\Phi })}=1+2v_2cos(2(\varphi \mathrm{\Phi }))`$. The values of the $`v_2`$ parameter are linearly parameterized as a function of $`p_T`$ and centrality using PHENIX measurements of inclusive charged hadrons phenixFlow . Only generated particles that lie within the PHENIX azimuthal acceptance are included in the calculation of $`M_{p_T}`$. This simulation estimates that the contribution of elliptic flow to $`F_{p_T}`$ is largely cancelled out by the symmetry of the PHENIX acceptance, and is negligible for central collisions. The estimated elliptic flow contribution to the value of $`F_{p_T}`$ is less than 0.1% for $`N_{part}>150`$, increasing to about 0.6% for $`N_{part}<100`$. Note that $`F_{p_T}`$ measured for minimum bias p+p collisions, where collective flow is not expected to contribute, is non-zero ($`1.9\pm 0.6\%`$), implying that a non-flow contribution may also be present in peripheral Au+Au collisions.

Figure 3 illustrates that a large contribution to the observed non-random fluctuations is due to the correlation of high $`p_T`$ particles, such as might be expected from correlations due to jet production Liu03 . In order to estimate the contribution due to jets, a Monte Carlo simulation is again applied. Events are generated with a Gaussian distribution of $`N_{tracks}`$ particles as independent particles that follow an $`m_T`$-exponential fit to the inclusive data $`p_T`$ distribution. Hard processes are defined to occur at a uniform rate per generated particle, $`S_{prob}(N_{part})`$, for each centrality class. This is the only parameter that is allowed to vary in the simulation. As Au+Au events are being generated, single $`\sqrt{s_{NN}}=200`$ GeV p+p hard-scattering events generated by the PYTHIA event generator PYTHIA  and filtered by the PHENIX acceptance are embedded into the event. The addition of the PYTHIA events affects the mean and standard deviation of the inclusive $`p_T`$ spectra by less than 0.1%. The value of $`F_{p_T}`$ has been extracted from 100,000 PYTHIA events for minimum bias p+p collisions, yielding $`F_{p_T}`$=2.06% within the PHENIX acceptance, which is consistent with the measured value of $`F_{p_T}=1.9\pm 0.6\%`$.

Two scenarios are considered for studies of the centrality-dependence of jet contributions to the value of $`F_{p_T}`$: 1) with $`S_{prob}(N_{part})`$ set at a constant rate for all centrality classes, and 2) with $`S_{prob}(N_{part})`$ scaled for each centrality class by the PHENIX measurement of the suppression of high $`p_T`$ charged particles, which is characterized by the nuclear modification factor, $`R_{AA}`$, integrated over $`p_T>4.5`$ GeV/c phenixSupp . The $`p_T`$ value at which $`R_{AA}`$ is extracted has little effect on the simulation results, which change by less than 0.2% for 0-5% centrality if the $`R_{AA}`$ measurement at $`p_T=2.0`$ GeV/c is used instead. The latter scenario is intended to model the effect of the suppression of jets due to energy loss in the nuclear medium Wang98  on the fluctuation signal. The initial value of $`S_{prob}(N_{part})`$ for both scenarios is normalized so that the $`F_{p_T}`$ result from the $`R_{AA}`$-scaled simulation matches that of the data for the 20-25% centrality class. The results of the simulation as a function of $`p_T^{max}`$, with $`S_{prob}(N_{part})`$ scaled by $`R_{AA}`$, are represented by the dashed curve in Fig. 3 for the 20-25% centrality class, The trend of increasing $`F_{p_T}`$ with increasing $`p_T^{max}`$ observed in the data is reproduced by the simulation reasonably well.

The results of the two hard scattering simulation scenarios are shown in Fig. 2 as a function of centrality. The model curves include the small contribution estimated from the elliptic flow simulation. The dotted curve is the result with $`S_{prob}(N_{part})`$ fixed for all centralities. The dashed curve is the result with $`S_{prob}(N_{part})`$ scaled by $`R_{AA}`$ as a function of centrality. Within this simulation, the decrease of $`F_{p_T}`$ for the more peripheral events is explained as a decrease in the signal strength relative to number fluctuations from the small and decreasing value of $`N_{tracks}`$. If $`S_{prob}(N_{part})`$ remains constant, the value of $`F_{p_T}`$ decreases only slightly when going from mid-central to central collisions, in contradiction with the large decrease seen in the data over this centrality range. When $`S_{prob}(N_{part})`$ is scaled by $`R_{AA}`$ as a function of centrality, the trend in the simulation of decreasing $`F_{p_T}`$ with increasing centrality is more consistent with the data.

To summarize, the PHENIX experiment has observed a positive non-random fluctuation signal in event-by-event average transverse momentum, measured as a function of centrality and $`p_T`$ in $`\sqrt{s_{NN}}=200`$ GeV Au+Au and p+p collisions. The increase of $`F_{p_T}`$ with increasing $`p_T`$ implies that the majority of the fluctuations are due to correlated high $`p_T`$ particles. A Monte Carlo simulation that includes elliptic flow and a PYTHIA-based hard scattering description can consistently describe contributions to the signal as a function of centrality and $`p_T`$ with a simple implementation of jet suppression.

We thank the staff of the Collider-Accelerator and Physics Departments at BNL for their vital contributions. We acknowledge support from the Department of Energy and NSF (U.S.A.), MEXT and JSPS (Japan), CNPq and FAPESP (Brazil), NSFC (China), CNRS-IN2P3 and CEA (France), BMBF, DAAD, and AvH (Germany), OTKA (Hungary), DAE and DST (India), ISF (Israel), KRF and CHEP (Korea), RMIST, RAS, and RMAE, (Russia), VR and KAW (Sweden), U.S. CRDF for the FSU, US-Hungarian NSF-OTKA-MTA, and US-Israel BSF.


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# Hard X-ray Emission Associated with White Dwarfs II.

## 1 Introduction

White dwarfs are not expected to emit X-rays at energies greater than 0.5 keV, but numerous white dwarfs appear to be associated with hard X-ray emission. Most of these white dwarfs with hard X-ray emission are in binary systems, and the hard X-rays originate from either the accretion of material from the companion onto the white dwarf or simply from the coronal activity of a late-type companion. A small number of white dwarfs with hard X-ray emission appear to be single, however. The most notable examples are WD 0005+511 (= KPD 0005+5106) and WD 1159$``$034 (= PG 1159). Their spectral types, DO and DQZO.4, suggest that the hard X-ray emission may be the high-energy Wien tail of emission from deep in the stellar atmosphere (O’Dwyer et al., 2003, hereafter Paper I).

In Paper I, we made a systematic search for white dwarfs with hard X-ray emission using the WGA catalog of ROSAT X-ray point sources (White, Giommi, & Angelini, 2000, hereafter WGACAT)111available at http://wgacat.gsfc.nasa.gov/wgacat/wgacat.html. and the list of white dwarfs from McCook & Sion (1999). This search was rendered incomplete because the WGACAT did not include ROSAT Position Sensitive Proportional Counter (PSPC) observations made with the boron filter. Furthermore, 214 white dwarfs discovered since 1999 were not included in Paper I. To improve the completeness, we have therefore repeated the search for white dwarfs with hard X-ray emission using an updated list of white dwarfs and the most complete catalogs of ROSAT X-ray sources. The extended results are reported in this paper.

## 2 Search for Hard X-ray Sources Associated with White Dwarfs

To search for hard X-ray sources associated with white dwarfs, we first cross-correlate the white dwarf catalog with the ROSAT X-ray source catalogs. The most complete list of known white dwarfs in the Galaxy is provided by the web version of McCook & Sion’s catalog222available at http://www.astronomy.villanova.edu/WDCatalog., which is continuously updated to include new white dwarfs and contains 2,449 white dwarfs at present. For the ROSAT X-ray sources, we use the final ROSAT Results Archive catalogs333available at http://wave.xray.mpe.mpg.de/rosat/catalogue, i.e., the Second ROSAT Source Catalog of Pointed Observations with the PSPC (2RXP), and the Second ROSAT Source Catalog of Pointed Observations with the PSPC with Filter (2RXF). We adopt the same criterion for positional coincidence used in Paper I, i.e., $`1^{}`$ offset between a white dwarf and an X-ray source. In addition to the coincidences reported in Table 1 of Paper I, we find 58 new X-ray sources apparently coincident with white dwarfs.

To confirm the coincidence between the white dwarfs and the ROSAT X-ray sources and to examine the X-ray spectral characteristics, we retrieved the ROSAT PSPC event files from the High Energy Astrophysics Science Archive Research Center at NASA’s Goddard Space Flight Center. For each PSPC observation, we extract images in the 0.1–0.5 keV (soft) and 0.55–2.0 keV (hard) energy bands, and compared them to optical images from the Digitized Sky Survey to determine (1) whether the X-ray source is coincident with the white dwarf or a background object projected in its vicinity, and (2) whether hard X-ray emission is present and coincident with the soft X-ray emission.

The results of our examination of the 58 white dwarfs with cataloged ROSAT X-ray sources within 1 are presented in Table 1. Columns 1–3 give the identifications, common names, and spectral types of the white dwarfs; columns 4–6 list the corresponding X-ray sources in the 2RXP or 2RXF catalogs, the $`ROSAT`$ PSPC observations used for the detection, and the exposure times of the PSPC observations; column 7 describes the positional coincidence between the X-ray source and the white dwarf and the detection of hard and soft X-ray emission; and columns 8–10 present the counts detected in the soft (0.11–0.41 keV), medium (0.52–0.9 keV), and hard (0.91–2.01 keV) bands, as reported in the internal files of the 2RXP or 2RXF catalogs.

Our examination shows that 11 of the 58 coincidences initially identified by cross-correlating the cataloged positions of white dwarfs and X-ray sources are spurious. These objects are noted in column 7 as U1–4. “U1” is noted when the X-ray source is not convincingly centered on the white dwarf: either the white dwarf is outside the point spread function of the X-ray source (WD 0757$``$606.2, WD 0949+495, WD 1103+384, and WD 1626+409) or the X-ray source is centered closer to a bright star whose spectral type is commonly associated with coronal activity (WD 1407$``$475). “U2” is noted if the X-ray source is just a weak peak on a bright background, and thus the source identification is ambiguous. “U3” is noted if a large number of candidates for optical counterpart are present within the PSPC’s point spread function. “U4” is noted if the X-ray source is too faint to be credible.

In column 7 of Table 1, we have further noted the detection of soft and hard X-ray emission by “S” and “H,” based on our examination of the PSPC image in the 0.1–0.5 keV and 0.5–2.4 keV bands, respectively. These notes should be more accurate assessments of the detection than the automated measurements given in the 2RXP and 2RXF catalogs especially for objects with background sources projected in the vicinity.

It can be seen from Table 1 that only five white dwarfs are coincident with X-ray sources (i.e., the white dwarf is well within the PSPC point spread function) and show hard X-ray emission. These five white dwarfs will be individually discussed in the next section. Note that Table 1 of this paper and the Table 1 in Paper I together represent the most complete summary of detection of X-ray emission from white dwarfs in ROSAT PSPC pointed observations. The list of white dwarfs detected in the ROSAT All Sky Survey has been reported by Fleming et al. (1996).

## 3 Description of Individual White Dwarfs with Hard X-rays

WD 0005+511 (KPD 0005+5106) was not identified in the survey of Paper I because its PSPC observation was made with a boron filter, but it was discussed in detail in Paper I. Briefly, the DOQZ.4 white dwarf WD 0005+511 is apparently single, with no near infrared excess emission, but it shows hard X-ray emission peaking at 1 keV.

WD 0220+222 (EGGR 18) is a visual companion of the G0 star HD 14784. The X-ray spectrum is similar to those commonly seen from stellar coronal sources. The hard X-ray emission is most likely associated with the G0 star HD 14784.

WD 0512+326 (14 Aur C; KW Aur C; HD 33959C) has a dominant soft X-ray component, but a hard X-ray component peaking at 0.8 keV is unambiguously detected. This X-ray source is coincident with the single-lined spectroscopic binary 14 Aur C (Hodgkin et al., 1993), which is itself the fainter companion to another single-lined spectroscopic binary, 14 Aur A$`=`$KW Aur, a $`\delta `$ Sct and ellipsoidal variable. The DA1.8 white dwarf responsible for the UV and soft X-ray emission is not detected at optical wavelengths, but is resolved at 2$`\stackrel{}{\mathrm{.}}`$0 from the primary of 14 Aur C in an HST WFPC2 $`F185W`$ UV image (Barstow et al., 2001). The primary component of 14 Aur C, an F4 V star, is in a short-period orbit ($`P=2\stackrel{\mathrm{d}}{\mathrm{.}}993`$: Webbink et al., 1992; Emley et al., 1996; Vennes, Christian, & Thorstensen, 1998) with an unseen companion. That companion is deduced (from the spectroscopic mass function and projected rotation velocity of the F4 V star) to be an $``$M0 V dwarf (Tokovinin, 1997; Webbink et al., 2001), making it the likely source of coronal hard X-ray emission.

WD 0907+336 is detected by a pointed PSPC observation at a 48 off-axis position with a very extended point spread function. A better position can be found in the ROSAT All Sky Survey Bright Source Catalog (Voges et al., 1999), where this X-ray source is designated as 1RXS J091037.2+332920. This X-ray source has been associated with a radio source and classified as a BL Lac object (White et al., 2000). Therefore, the X-ray source is likely unrelated to a white dwarf. Note that the classification of WD 0907+336 as a DC white dwarf based on its “featureless” optical spectrum (Wegner & Boley, 1993) was not confirmed by Everett & Wagner (1995). It is most likely that “WD 0907+336” is a misclassified BL Lac object. Such misclassification is not without precedent, as Fleming et al. (1993) have pointed out three other BL Lac objects that were formerly misclassified as DC white dwarfs.

WD 2226$``$210 is the central star of the Helix Nebula. It was not identified in the survey of Paper I because the white dwarf catalog of McCook & Sion (1999) had a sign error in the declination, which has been corrected in the web version of the catalog. WD 2226$``$210 shows hard X-ray emission but not near infrared excess. Based on the temporal variations of its hard X-ray emission and H$`\alpha `$ emission line profile, it has been suggested that WD 2226$``$210 possesses a late-type dMe companion, and that the dMe star’s coronal activity is responsible for the hard X-ray emission (Gruendl et al., 2001; Guerrero et al., 2001).

## 4 Discussion and Conclusions

We have completed a search for ROSAT PSPC X-ray sources coincident with white dwarfs. Paper I reported the results from cross-correlating the white dwarfs cataloged by McCook & Sion (1999) and the X-ray sources detected in pointed PSPC observation without a boron filter (WGACAT). The current paper reports PSPC X-ray sources coincident with white dwarfs that were discovered after 1999 or white dwarfs that are detected only in PSPC observations made with the boron filter. Therefore, Table 1 of Paper I and Table 1 of this paper represent a complete summary of pointed ROSAT PSPC observations of white dwarfs with and without filter.

Table 1 lists 47 cases in which a PSPC source is convincingly coincident with a white dwarf. Among these X-ray sources, 5 show hard X-ray emission. Three of these have confirmed or suggested late-type companions that are likely responsible for the hard X-ray emission, one is apparently single, and the other is a misclassified BL Lac object. The fraction of white dwarfs with apparent hard X-ray emission in this sample (excluding the misclassified BL Lac object), 4/46 $``$ 9%, is lower than that for the sample in Paper I, 17/76 $``$ 22%. These different detection rates are probably caused by the different exposure times of PSPC observations. Column 6 of Table 1 shows that most of the PSPC observations have short exposure times, less than 10 ks. As shown in Paper I, hard X-ray sources associated with white dwarfs are much finater than the soft X-ray emission from the white dwarfs themselves; in the most interesting cases, the hard X-ray count rate is $``$1% of the soft X-ray count rate, for example, PG 1159. Deep exposures are needed to detect the faint hard X-ray emission from white dwarfs, especially teh apparently single ones.

No apparently single white dwarfs with hard X-ray emission are discovered beyond those included in the discussion of Paper I. The most intriguing conclusion of paper I is the possibility of a photospheric origin for the hard X-ray emission from hot DO and DQZO white dwarfs, i.e., KPD0005+5106 and PG 1159. To confirm this possibility, it is necessary to rule out the existence of a faint, late-type dMe companion. It is possible to diagnose the existence of a dMe companion using the temporal and spectral properties of the hard X-ray emission as well as the temporal variations of the H$`\alpha `$ emission line. High-quality near infrared spectra may also reveal absorption lines from a late-type companion. These follow-up observations are essential to confirming or rejecting the photospheric origin of hard X-ray emission from apparently single hot white dwarfs.

We gratefully acknowledge the support of the NASA ADP grant NAG 5-13076. We also thank the anonymous referee for useful suggestions to improve the paper. This research has made use of the SIMBAD database, operated at CDS, Strasbourg, France, and the Digital Sky Survey produced at the Space Telescope Science Institute under U.S. Government grant NAG W-2166. We have also used data product from the 2MASS, which is a joint project of the University of Massachusetts and the Infrared Processing and Analysis Center/California Institute of Technology, funded by NASA and NSF.


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# Is the Quantum Hall Effect influenced by the gravitational field?

(13 October 2003)

## Abstract

Most of the experiments on the quantum Hall effect (QHE) were made at approximately the same height above sea level. A future international comparison will determine whether the gravitational field $`𝐠(x)`$ influences the QHE. In the realm of (1 + 2)-dimensional phenomenological macroscopic electrodynamics, the Ohm-Hall law is metric independent (‘topological’). This suggests that it does not couple to $`𝐠(x)`$. We corroborate this result by a microscopic calculation of the Hall conductance in the presence of a post-Newtonian gravitational field.

An experiment done in Grenoble, France, on the Quantum Hall Effect (QHE) — does it yield the same result as a corresponding experiment done in Boulder, Colorado? Recall that in Grenoble the height above sea level is about 220 m whereas Boulder lies at about 1600 m. For two atomic clocks situated in Grenoble and Boulder, respectively, this difference in heights, and thus the difference in the gravitational potential, yields a measurable effect on the time keeping process Will . The clock in Grenoble runs slow as compared to the Boulder clock. Accordingly, the influence of the gravitational field on effects in atomic physics is an established fact and it seems legitimate to ask whether the QHE is also affected by the gravitational field $`𝐠=\phi `$, with $`\phi `$ as potential. The Hall conductance may then depend on the dimensionless quantity $`\phi /c^2`$.

The QHE is a fascinating manifestation of quantum mechanics on the macroscopic levelprangegirvin ; Hajdu . An important ingredient of the theoretical explanation of the QHE is the idea that the quantized Hall conductance can be linked to a topological invariant, the Chern numberThouless ; physicstoday . The topological interpretation suggests that the Quantum Hall Resistance (QHR) should be very robust against perturbations. Indeed, its excellent reproducibility makes the QHR very suitable for metrological purposes.FlowersPetley ; MohrTaylor ; Uzan ; Honnef  As pointed out by Jeckelmann and JeanneretJeckelmannJeanneret , the reproducibility of the QHR has been established at different locations with a precision of about $`5\times 10^8`$. However, the locations at which these QHRs were measured are all at about the same height, namely Gaithersburg, USA (NIST), London (NPL), Sydney (NML)Jeckelmann . Therefore, in future one should compare the results on the QHR as a function of height. This is what we would like to suggest.

What outcome do we expect? We will advance a macroscopic argument that the QHE and the QHR should be completely independent of the gravitational potential and will present a microscopic calculation in support of this view.

Conductor in a gravitational field. The idea that the gravitational field may affect the conductive properties of matter, in particular those of normal metals or superconductors, is a direct consequence of the fact that charges (here electrons and ions) carry mass and energy. Since gravity is universally coupled to the energy-momentum of matter, it also acts on the electric currents and the electromagnetic fields in conductors. Because of the equivalence principle, the same qualitative effects should be caused by gravitational as well as by inertial forces. This was analyzed for accelerating (rotating) conductors,noninert ; super1 ; Ohmlaw  and for the gravitational analog of the Hall effect.gravhall

Electrodynamics in a four-dimensional spacetime “feels” inertial and gravitational effects via the metric-dependent constitutive (spacetime and material) relations. For conductors, this is manifest in the covariant generalization of Ohm’s law Ohmlaw . We can use a macroscopic phenomenological picture in order to estimate the possible magnitude of the gravitational effects. For isotropic matter with conductance $`\sigma `$, which is at rest in a Cartesian reference frame, the electric current density 3-vector $`j^a`$ of the free charges, with $`a=1,2,3`$, is related to the electric field $`E_a`$ by means of Ohm’s law

$$j^a=\sigma g^{ab}E_a.$$
(1)
Here $`g^{ab}`$ is the spatial part of the 4-dimensional spacetime metric $`g^{ij}`$. In the gravitational Schwarzschild field of the Earth with mass $`M`$, we have

$$g^{ab}=\left(1+\frac{GM}{2c^2r}\right)^4\delta ^{ab}(12\phi /c^2)\delta ^{ab},$$
(2)
with $`\phi =GM/r`$. Consequently, when the electric field and the current are measured for a conductor not in a flat space with the Euclidean 3-metric $`g^{ab}=\delta ^{ab}`$, but in a curved spacetime of the Earth, the classical longitudinal conductance will be modified by the gravitational field to the effective conductivity $`\sigma ^{}=(12\phi /c^2)\sigma `$. The resulting effect with a relative change of about $`10^9`$ is close to the present accuracy of quantum Hall measurements.

This estimate is based on the macroscopic approach. Another possible manifestation of gravity in conductors arises from the microscopic analysis of the redistribution of charges in conducting matter under the influence of the gravitational or inertial forces. Such a redistribution leads to the emergence of weak electric and magnetic fields near the surface of and inside metallic bodiesinduced ; review . For a conductor in a gravitational field $`𝐠`$, the resulting induced electric field is $`𝐄0.1(m_i/e)𝐠`$, where $`e`$ is the elementary charge and $`m_i`$ the mass of the ion in the conductor’s lattice.

Electrodynamics in 1 + 2 dimensions. Since the 1960s, experimentalists were able to create a 2-dimensional electron gas (2DEG) in suitable transistors at sufficiently low temperatures and to position it in a strong external transversal magnetic field $`B`$. Then, the electrons can only move in a plane transverse to $`B`$ and one space dimension can be suppressed. Therefore a $`(1+2)`$-dimensional version of Maxwell’s equations would be appropriate for describing this situation.

We start from the Maxwell equations valid in any spacetime dimension. In exterior calculus, they can be given compactly asbirkbook  $`dG=J`$ and $`dF=0`$, with $`G`$ as electromagnetic excitation, $`J`$ as electric current, and $`F`$ as electromagnetic field strength. In tensor language,Schouten  they read

$$_k𝒢^{ik}=𝒥^i,_iF_k\mathrm{}+_kF_\mathrm{}i+_{\mathrm{}}F_{ki}=0,$$
(3)
with $`𝒢^{ik}=𝒢^{ki}`$ and $`F_{ik}=F_{ki}`$. This “premetric” form of the Maxwell equations is totally independent of the metric. As a consequence, all field quantities have different transformation properties: The $`𝒥^i`$ is a contravariant 3-vector density, $`𝒢^{ik}`$ an antisymmetric contravariant 3-tensor density, and $`F_{ik}`$ a antisymmetric covariant 3-tensor.

In $`1+2`$ spacetime dimensions, the indices $`i,k,\mathrm{}`$ in (3) run from $`0`$ to $`2`$. Then the currents and the fields can be expressed in terms of their 2-dimensional quantities,

$`(𝒥^i)=\left(\begin{array}{c}\rho \\ j^1\\ j^2\end{array}\right),(𝒢^{ik})`$ $`=`$ $`\left(\begin{array}{ccc}0& 𝒟^1& 𝒟^2\\ 𝒟^1& 0& \\ 𝒟^2& & 0\end{array}\right),`$
$`(F_{ik})`$ $`=`$ $`\left(\begin{array}{ccc}0& E_1& E_2\\ E_1& 0& B\\ E_2& B& 0\end{array}\right),`$ (4)
with the area densities of charge $`\rho `$ and current $`(j^1,j^2)`$, the magnetic and electric excitations $``$ and $`(𝒟^1,𝒟^2)`$, and electric and magnetic field strengths $`(E_1,E_2)`$ and $`B`$, respectively.

We substitute (Is the Quantum Hall Effect influenced by the gravitational field?) into (3) and find

$`_1𝒟^1+_2𝒟^2=\rho ,`$ $`_2\dot{𝒟}^1=j^1,_1\dot{𝒟}^2=j^2,`$ (5)
$`_1E_2_2E_1+\dot{B}=0.`$
The $`\mathrm{div}B=0`$ equation is degenerate and drops out. We assumed an infinite extension of the 2DEG. If this is no longer a valid approximation, one has to allow for line currents at the boundary of the sample (“edge currents”) in order to fulfill the Maxwell equations.

Being interested in the phenomenology of the QHE, we have to connect in (3) somehow the current $`𝒥^i`$ with the field strength $`F_{ik}`$ by a constitutive law. The linear ansatz of the Ohm-Hall law,Frohlich ; birkbook

$$𝒥^i=\sigma ^{ik\mathrm{}}F_k\mathrm{}$$
(6)
links both quantities in a generally covariant form, provided the Hall conductance $`\sigma ^{ik\mathrm{}}=\sigma ^{i\mathrm{}k}`$ is a contravariant 3-tensor density of rank 3. The totally antisymmetric Levi Civita symbol $`ϵ^{ik\mathrm{}}=\pm 1,0`$ has the same transformation property as a tensor density.

Accordingly, if we assume isotropy in 3 dimensions, we have, with the scalar field $`\sigma _\mathrm{H}`$,

$$𝒥^i=\sigma _\mathrm{H}ϵ^{ik\mathrm{}}F_k\mathrm{}/2$$
(7)
or, decomposed in time and space,

$$\rho =\sigma _\mathrm{H}B,j^1=\sigma _\mathrm{H}E_2,j^2=\sigma _\mathrm{H}E_1.$$
(8)
These are classical phenomenological laws which need some interpretation when applied to the description of a quantum system. Within a classical electron model for the conductivity, one finds for the Hall conductivity $`\sigma _\mathrm{H}=\frac{\rho }{B}`$. This relation is expressed in (7) in generally covariant form with a scalar conductivity $`\sigma _\mathrm{H}`$ and with the additional information of a vanishing longitudinal conductivity. However, a vanishing longitudinal conductivity is found in the plateau region of a quantum Hall system, where the Hall conductivity is given by the classical value for a charge density $`\rho =\frac{1}{N}\frac{e^2}{h}B`$, which corresponds to $`N`$ completely filled Landau levels. The quantum mechanical input is the robustness of this phenomenology against the influence of disorder and against density variations. With this additional input, the complete independence of the quantum Hall resistance of the gravitational field can be concluded from (7).

We differentiate (7) by $`_i`$. Then, because of $`_i𝒥^i=0`$ and $`ϵ^{ik\mathrm{}}_iF_k\mathrm{}=0`$,

$$_i\sigma _\mathrm{H}=0,$$
(9)
that is, the Hall conductance is constant in time and space. In turn, if we substitute (7) into the right-hand-side of $`_k𝒢^{ik}=𝒥^i`$, it can be integrated and yields

$$𝒢^{ik}=ϵ^{ik\mathrm{}}\sigma _\mathrm{H}A_{\mathrm{}},$$
(10)
with the electromagnetic potential defined by $`F_k\mathrm{}=_kA_{\mathrm{}}_{\mathrm{}}A_k`$. The integration constant is irrelevant since the potential is not uniquely determined anyway. Eq.(6) is a remarkable constitutive law that is in clear contrast to the standard $`𝒢^{ik}=\sqrt{g}g^i\mathrm{}g^{km}F_\mathrm{}m`$ law of (1+3)-dimensional vacuum electrodynamics. Eq.(10) represents a 3-dimensional Chern-Simons electrodynamics.

Microscopic analysis of the gravitational field dependence of the QHE. The theoretical analysis presented in this section is concerned with the integer QHE only, whereas the macroscopic argument discussed in the previous section is applicable to both, the integer and fractional QHE. A magnetic field perpendicular to a two-dimensional electron system leads to a quantization of states in Landau levels (LLs) at energies $`E_n=(n+1/2)\mathrm{}\omega _c`$, with $`\omega _c=eB/m`$. The density of states (DoS) is $`\rho (E)=_n\delta (EE_n)B/\mathrm{\Phi }_0`$, where the last factor describes the macroscopic degeneracy of an LL. Here, $`\mathrm{\Phi }_0=h/e`$ denotes the magnetic flux quantum. Thus, a system with a completely filled highest LL is characterized by a mobility gap $`\mathrm{}\omega _c`$. For the Hall resistance of a system with $`N`$ completely filled LLs one finds the value $`\frac{1}{N}\frac{h}{e^2}`$, and as a function of the chemical potential, the Hall resistance follows a stair step curve with plateaus at exactly these values.

Impurities in real samples lead to a broadening of the delta function peaks in the DoS, i.e., the disappearance of the excitation gap. In addition, electronic states become localized with exception of a region of delocalized states centered around $`E=E_n`$. As a consequence, the excitation gap of the clean system is replaced by a mobility gap in the disordered system, which leads to a stair step curve of the Hall resistance as a function of the magnetic field or the electron density. Due to the topological nature of the quantum Hall resistance as an integral over the Brillouin zone, the value of the plateau resistance is unchanged as compared to the clean system Thouless ; physicstoday .

Real samples are finite and have contacts. The sample boundaries are described by a confining potential that prevents the electrons from leaving the sample and leads to the formation of one–dimensional edge states Halperin82 . Theoretically, these edge states can be modelled as ideal one–dimensional wires, and assuming the above described localization–delocalization scenario for the bulk states, one can derive the quantized Hall resistance in the framework of the Landauer–Büttiker approach Buettiker88 . The current distribution in real experiments is not restricted to narrow channels along the sample edges but generally involves delocalized bulk states as well. For this reason, both the Hall resistivity of bulk states and the resistance of edge states need to be combined for a complete description of experimental results Hajdu .

For reasons of simplicity, we will ignore both disorder and edge effects first. We make a quantitative prediction of the influence of gravitational corrections on the Hall resistance of a clean system with a completely filled highest LL. In addition, we present a qualitative argument why the result of this calculation should be valid in the presence of edge states and disorder as well. The influence of gravity up to order $`g/c^2`$ is described by the Hamiltonian HehlNi

$$\widehat{H}_{\mathrm{grav}}=m\phi (\widehat{𝐱})\frac{1}{2m}\widehat{𝐩}\frac{\phi (\widehat{𝐱})}{c^2}\widehat{𝐩}\frac{\mathrm{}}{4mc^2}\widehat{\sigma }(\phi (\widehat{𝐱})\times \widehat{𝐩}).$$
(11)
We first discuss the situation where $`\phi (𝐱)`$ is perpendicular to the plane of the 2DEG. Labeling the plane of the 2DEG as the $`xy`$–plane, the gravitational potential depends on $`z`$ only and hence commutes with $`\widehat{p}_x`$ and $`\widehat{p}_y`$. The first term in $`\widehat{H}_{\mathrm{grav}}`$ turns into a constant which contributes an oscillatory time dependence to the wave functions. The second term, which describes the gravitational redshift of the kinetic energy, does not depend on position any more and only modifies the effective mass of the electrons, which drops out of the calculation of the Hall resistance. The third term is analogous to the Rashba term Rashba60  $`\gamma \widehat{\sigma }(i\times 𝐄)`$, which describes the influence of the confining electric field on the electron spin. The Rashba term is not known to influence the accuracy of the integer QHE. In addition, the coupling strength $`\gamma E10^{12}eVm`$ is about 23 orders of magnitude larger than the gravitational coupling $`\frac{\mathrm{}^2g}{4mc^2}10^{35}eVm`$. In conclusion, there is no evidence that a gravitational field perpendicular to the plane of the 2DEG influences the Hall resistance to order $`\phi /c^2`$.

Next, we assume $`𝐠(𝐱)`$ to be in the plane of the 2DEG. The electric field needed to counteract the gravitational force is $`E=mg/e10^{10}V/m`$ and hence about ten orders orders of magnitude smaller than the Hall electric field in metrological applications. The influence of the gravitational field on the ions in a conductor is stronger by a factor of $`10^2`$ and hence more important for actual measurements. The “gravitational Rashba term” in (11) is again dominated by the corresponding term due to the externally applied electric field. To discuss the gravitational redshift of the kinetic energy, we assume $`𝐠`$ to be oriented along the negative $`x`$–direction and use a Taylor expansion $`\phi (𝐱)=\phi _0gx`$. We consider a torus with finite extension $`L_y`$ in $`y`$–direction and infinite extension in $`x`$–direction.

Using the Landau gauge $`𝐀(𝐱)=(0,Bx,0)`$, we make the usual product ansatz of a plane wave of momentum $`k`$ in $`y`$–direction and a $`x`$–dependent $`\psi _\alpha (x)`$, with $`\alpha =(n,k)`$ denoting the set of quantum numbers. Upon inserting this ansatz into the full Schrödinger equation, the effective Hamiltonian for $`\psi _\alpha (x)`$, in the presence of an electric field $`E`$ in $`x`$–direction, reads

$`H_x`$ $`=`$ $`{\displaystyle \frac{1}{2}}\widehat{p}_x({\displaystyle \frac{1}{m}}+{\displaystyle \frac{gx}{mc^2}})\widehat{p}_x+{\displaystyle \frac{1}{2}}m\omega _c^2(xX)^2`$
$`+`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \frac{gm\omega _c^2}{c^2}}x(xX{\displaystyle \frac{eE}{m\omega _c^2}})^2+eEX+{\displaystyle \frac{e^2E^2}{2m\omega _c^2}}.`$
Here, $`X=\frac{\mathrm{}k}{eB}\frac{eE}{m\omega _c^2}`$. The current in $`y`$–direction of a state $`\mathrm{\Psi }_\alpha `$ can be calculated as the derivative

$$I_y=e\alpha |\widehat{v}_y|\alpha =(1/eB)ϵ_\alpha /X.$$
(13)
To order $`O(g/c^2)`$, a perturbative evaluation of the corresponding terms in the Hamiltonian (Is the Quantum Hall Effect influenced by the gravitational field?) is sufficient. As we want to discuss the influence of disorder and a boundary potential, we first use a transformation which turns the position dependent effective mass (first term in (Is the Quantum Hall Effect influenced by the gravitational field?))

$$1/m(x)=1/m+gx/(mc^2)$$
(14)
into an effective potential. Following Gonul et al.Go+02 , the position dependent effective mass is replaced by a constant mass $`m_0`$ by applying a coordinate transformation $`x=f(\stackrel{~}{x})`$ whose inverse is defined by $`\stackrel{~}{x}=_0^x𝑑u\sqrt{m(u)/m_0}=f^1(x)`$. This coordinate transformation leaves the spectrum of the Hamiltonian unchanged but renormalizes the wave function and changes the potential $`V(x)`$ to an effective potential $`V_{eff}(\stackrel{~}{x})`$. To order $`O(g/c^2)`$, we find

$$V_{eff}(\stackrel{~}{x})=V(f(\stackrel{~}{x}))+O((g/c^2)^2).$$
(15)
An evaluation of the energy shift due to the gravitational corrections yields the current density

$$j_y=\frac{e^2}{h}E_x\left(1+\frac{g}{c^2}\frac{eE_x}{m\omega _c^2}\right)+\frac{eg}{hc^2}\mathrm{}\omega _c(n+\frac{1}{2})$$
(16)
for a completely filled $`n`$–th LL. The constant background current (last term) is, with $`10^{23}A`$, much smaller than the typical experimental currents of about $`10^7A`$. The nonlinear correction to the Hall conductivity for typical values of the electric field is about $`10^{19}`$ and does not influence experimental results.

The change of the disorder potential due to the transformation (15) is reflected in the change of the correlation function for the disorder potential. However, as the details of the disorder correlator are known to be irrelevant for the derivation of quantum Hall plateaus, we conjecture that the gravitational terms do not change the localization–delocalization scenario responsible for the integer QHE. Similarly, the formation of edge states does not depend on the details of the confining potential, and we find it unlikely that the qualitative properties of edge states are changed by the transformation (15).

In summary, our calculations suggest that the linear Hall resistance is not influenced by a gravitational field to order $`O(g/c^2)`$. This finding corroborates the idea arising from a macroscopic argument that the Hall resistance may be completely independent of the gravitational field. For a field orientation parallel to the 2DEG, we find both a constant background current and a nonlinear contribution to the Hall current. The only term which is possibly relevant for experiment is the background voltage caused by the gravitational potential. This contribution could be detected with an experimental accuracy of $`10^8`$.

Acknowledgments. We appreciate a discussion that we had with K. von Klitzing (Stuttgart) on the QHE and, in particular, on its possible dependence on the gravitational field. Moreover, we thank R. Klesse (Cologne) for valuable remarks and M. Kelly (NIST) for providing helpful information. This project has been supported by the grant HE 528/20-1 of the DFG (Bonn).


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# Structure and stability of copper clusters : A tight-binding molecular dynamics study

## I Introduction

The study of clusters has become an increasingly interesting topic of research in both physics and chemistry in recent years, since they span the gap between the microscopic and macroscopic materials heer ; brack . Metallic clusters play a central role in catalysis valden ; kink1 ; joo ; hansen  and nanotechnology binns ; park1 ; gittins . Cluaters of coinage metals $`Cu`$, $`Ag`$ and $`Au`$ have been used in a wide range of demonstration valden ; kink1 ; joo ; hansen ; binns ; park1 ; gittins . The determination of structural and electronic properties and the growth pattern of coinage metal clusters are of much interest both experimentally katakuse ; tigges ; apai ; balerna ; montano ; taylor ; ho ; knickelbein ; spasov  and theoretically massobrio ; calaminici ; akeby ; kabir ; datta ; gda . The electronic configuration of the coinage metals are characterized by a closed $`d`$ shell and a single $`s`$ valance electron \[$`Cu:Ar(3d)^{10}(4s)^1`$, $`Ag:Kr(4d)^{10}(5s)^1`$, $`Au:Xe(5d)^{10}(6s)^1`$\]. Due to the presence of single $`s`$ electrons in the atomic outer shells, the noble metal clusters are expected to exhibit certain similarities to the alkali metal clusters. Electronic structure of alkali metal clusters are well described by the spherical shell model, which has successfully interpreted the “magic numbers” in $`Na_n`$ and $`K_n`$ clusters heer ; brack . A number of experimental features of noble metal clusters are also qualitatively well described in terms of simple $`s`$ electron shell model. For instance, the mass abundance spectrum of $`Cu_n^{}`$, $`Ag_n^{}`$ and $`Au_n^{}`$ clusters, which reflects the stability of clusters, can be explained by the one-electron shell model katakuse . But some experimental studies tigges ; apai ; balerna ; montano  indicate that the localized $`d`$ electrons of the noble metals play a significant role for the geometrical and electronic structure through the hybridization with more extended valence $`s`$ electron . Therefore, it is important to include the contribution of $`3d`$ electrons and the $`sd`$ hybridization for $`Cu_n`$ clusters.

Bare copper clusters in the gas phase have been studied experimentally by Taylor et al. taylor  and Ho et al. ho  using photoelectron spectroscopy (PES). Knickelbein measured ionization potentials of neutral copper clusters and found evidence of electronic shell structure knickelbein . Very recently cationic copper clusters have been studied using threshold collision-induced dissociation (TCID) by Spasov et al. spasov . Copper clusters have been also investigated theoretically by various accurate quantum mechanical and chemical approaches. Massobrio et al. massobrio  studied the structures and energetics of $`Cu_n`$ ($`n=2,3,4,6,8,10`$) within the local density approximation of density functional theory (DF-LDA) by using the Car Parinello (CP) method. Calaminici et al.  calaminici  used the linear combination of Gaussian-type orbitals density functional (LCGTO-DFT) approach to study $`Cu_n`$, $`Cu_n^{}`$ and $`Cu_n^+`$ clusters with $`n5`$. Akeby et al. akeby  used the configuration interaction (CI) method with an effective core potential (ECP) for $`n10`$. In an earlier communication kabir  we studied the small $`Cu_n`$ clusters for $`n9`$ by using full-potential muffin-tin orbitals (FP-LMTO) technique.

Ideally, the sophisticated, quantum chemistry based, first-principles methods predict both the stable geometries and energetics to a very high degree of accuracy. The practical problem arises from the fact that for actual implementation these techniques are limited to small clusters only. None of the methods described above can be implemented for clusters much larger than $``$ 10 atoms, because of prohibitive computational expense. The aim of this communication is to introduce an semi-empirical method, which nevertheless retains some of the electronic structure features of the problem. The empirical parameters are determined from first-principles calculations for small clusters, and corrections introduced for local environmental corrections in the larger clusters.

In recent years empirical tight-binding molecular dynamics (TB-MD) method has been developed as an alternative to ab initio methods. As compared with ab initio methods, the parameterized tight-binding Hamiltonian reduces the computational cost dramatically. The main problem with the empirical tight-binding methods has always been the lack of transferability of its empirical parameters. We shall describe here a technique that allows us to fit the parameters of the model from a fully ab initio, self-consistent local spin-density approximation (LSDA) based FP-LMTO calculation reported earlier by us kabir ; datta  for the smaller clusters and then make correction for the new environment for clusters in order to ensure transferability (at least to a degree).

It should be mentioned here that Copper clusters have also been investigated by other empirical methods. D’Agostino carried molecular dynamics using a quasi-empirical potential derived from a tight-binding approach for nearly 1300 atoms gda . More recently Darby et al. carried geometry optimization by genetic algorithm using Gupta potential gupta  for $`Cu_n`$, $`Au_n`$ and their alloy clusters in the size range $`n56`$ darby . These kinds of empirical atomistic potentials are found to be good to predict ground state geometries but can not predict electronic properties such as electronic shell closing effect for $`n=`$$`2`$, $`8`$, $`20`$, $`40`$, $`\mathrm{}`$, highest occupied-lowest unoccupied molecular level (HOMO-LUMO) gap energy and ionization potential. Our proposed TBMD scheme will allow us to extrapolate to the larger clusters to study both the ground state geometries as well as ground state energetics as a function of cluster size.

Menon et al. have proposed a minimal parameter tight-binding molecular dynamics (TBMD) scheme for semiconductors menon1 ; menon2 ; ordejon  and extended the method for transition metal ($`Ni_n`$ and $`Fe_n`$) clusters menon3 ; menon4 . Recently Zhao et al. has applied this method for silver clusters zhao1 . In the present work, we shall introduce a similar TB model for copper.

Using this TBMD method, we shall investigate the stable structures, cohesive energies, relative stabilities, HOMO-LUMO gaps and ionization potentials of $`Cu_n`$ clusters in the size range $`n55`$. We shall indicate the comparison between the present results for small clusters, $`n9`$, with those of our previous FP-LMTO calculations and other ab initio and available experimental results. This is essential before we go over to the computationally expensive study of larger clusters.

## II Computational Method

Menon et al. introduced a minimal parameter tight-binding molecular dynamics (TBMD) scheme for transition metal clusters menon3 ; menon4 . Here we will describe the main ingredients. In this tight-binding scheme the total energy $`E`$ is written as a sum,

$$E=E_{el}+E_{rep}+E_{bond}.$$
(1)
$`E_{el}`$ is the sum of the one-electron energies for the occupied states $`ϵ_k`$,

$$E_{el}=\underset{k}{\overset{occ}{}}ϵ_k,$$
(2)
where the energy eigenvalues $`ϵ_k`$ are calculated by solving the eigenvalue equation

$$H|\mathrm{\Psi }_k=ϵ_k|\mathrm{\Psi }_k,$$
(3)
where $`H`$ is the one-electron Hamiltonian and $`|\mathrm{\Psi }_k`$ is electronic wave function for $`k`$th level of the eigenstate. In the TB formulation, the single particle wavefunctions $`|\mathrm{\Psi }_k`$ are cast as a linear combination of orthogonalized basis functions $`\mathrm{\Phi }_{i\nu }`$, in the minimum basis set ($`\nu =s,p_x,p_y,p_z,d_{xy},d_{yz},d_{zx},d_{x^2y^2},d_{3z^2r^2}`$),

$$|\mathrm{\Psi }_k=\underset{i\nu }{}c_{i\nu }^k|\mathrm{\Phi }_{i\nu },$$
(4)
where $`i`$ labels the ions.

The TB Hamiltonian $`H`$ is constructed within Slater-Koster scheme slater , where the diagonal matrix elements are taken to be configuration independent and the off-diagonal matrix elements are taken to have Slater-Koster type angular dependence with respect to the inter-atomic separation vector $`𝐫`$ and scaled exponentially with the inter-atomic separation $`r`$:

$$V_{\lambda ,\lambda ^{^{}},\mu }=V_{\lambda ,\lambda ^{^{}},\mu }(d)S(l,m,n)exp[\alpha (rd)],$$
(5)
where $`d`$ is the equilibrium bond length for the fcc bulk copper, $`S(l,m,n)`$ is the Slater-Koster type function of the direction cosines $`l,m,n`$ of the separation vector $`𝐫`$ and $`\alpha `$ is an adjustable parameter ($`=2/d`$) menon4 .

The Hamiltonian parameters are determined from the dimensionless universal parameters $`\eta _{\lambda ,\lambda ^{^{}},\mu }`$ harrison ,

$$V_{\lambda ,\lambda ^{^{}},\mu }(d)=\eta _{\lambda ,\lambda ^{^{}},\mu }\left(\frac{\mathrm{}^2r_d^\tau }{md^{\tau +2}}\right),$$
(6)
Where $`r_d`$ is characteristic length for the transition metal and the parameter $`\tau =0`$ for $`ss`$, $`sp`$ and $`pp`$ interactions, $`\tau =3/2`$ for $`sd`$ and $`pd`$ interactions and $`\tau =3`$ for $`dd`$ interaction. In Table 1 we present the parameter $`r_d`$, the on-site energies $`E_s,E_p,E_d`$ and the universal constants $`\eta _{\lambda ,\lambda ^{^{}},\mu }`$ for Cu harrison . According to Ref.menon3  and Ref.menon4 , we set $`E_s=E_d`$ and $`E_p`$ large enough to prevent $`p`$-orbital mixing harrison . This choice of our tight-binding parameters reproduces the band structure of the fcc bulk Cu crystal given by Harrison harrison .

The repulsive energy $`E_{rep}`$ is described by a sum of short-ranged repulsive pair potentials, $`\varphi _{ij}`$, which scaled exponentially with inter-atomic distance,

$`E_{rep}`$ $`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle \underset{j(>i)}{}}\varphi _{ij}(r_{ij})`$ (7)
$`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle \underset{j(>i)}{}}\varphi _0exp[\beta (r_{ij}d)],`$
where $`r_{ij}`$ is the separation between the atom $`i`$ and $`j`$ and $`\beta (=4\alpha )`$ is a parameter. $`E_{rep}`$ contains ion-ion repulsive interaction and correction to the double counting of the electron-electron repulsion present in $`E_{el}`$. The value of $`\varphi _0`$ is fitted to reproduce the correct experimental bond length of the Cu dimer $`2.22`$ Å aslund  is given in Table2.

The first two terms of the total energy are not sufficient to exactly reproduce cohesive energies of dimers through bulk structures. Tomaǹek and Schluter tomanek  introduced a coordination dependent correction term, $`E_{bond}`$, to the total energy, which does not contribute to the force, it is added to the total energy after the relaxation has been achieved. However, for the metal clusters, this correction term is significant in distinguishing various isomers for a given cluster menon4 .

$$E_{bond}=n\left[a\left(\frac{n_b}{n}\right)^2+b\left(\frac{n_b}{n}\right)+c\right],$$
(8)
where $`n`$ and $`n_b`$ are the number of atoms and total number of bonds of the cluster respectively. Number of bonds $`n_b`$ are evaluated by summing over all bonds according to cut-off distance $`r_c`$ and bond length

$$n_b=\underset{i}{}\left[exp\left(\frac{r_{ij}r_c}{}\right)+1\right]^1.$$
(9)
The parameters $`a`$, $`b`$ and $`c`$ in the equation (6) are then calculated by fitting the coordination dependent term, $`E_{bond}`$, to the ab initio results for three small clusters of different sizes according to the following equation

$$E_{bond}=E_{\mathrm{𝑎𝑏𝑖𝑛𝑖𝑡𝑖𝑜}}E_{el}E_{rep}.$$
(10)
Thus we have four parameters $`\varphi _0`$, $`a`$, $`b`$, and $`c`$ in this TB model. These parameters are once calculated (given in the Table 2) for small clusters to reproduce known results (whatever experimental or theoretical) and then kept fixed for other arbitrary size cluster. To determine the parameters $`a,b`$ and $`c`$ we use the experimental binding energy of Cu dimer 1.03 eV/atom aslund  and the ab initio FP-LMTO results for $`Cu_4`$ and $`Cu_6`$ in Ref. kabir . For the $`Cu_2`$ dimer calculated vibrational frequency ($`226`$ cm-1) has reasonable agreement with experiment huber  ($`265`$ cm-1).

In molecular dynamics scheme the trajectories $`\{R_j(t)\}`$ of the ions are determined by the potential energy surface $`E[\{R_j(t)\}]`$ corresponding to the total energy of the electronic system. The force acting on the $`i`$-th ion is thus given by,

$`𝐅_i`$ $`=`$ $`_{R_i}E[\{R_j\}]`$ (11)
$`=`$ $`_{R_i}\left[{\displaystyle \underset{k}{}}\mathrm{\Psi }_k|H|\mathrm{\Psi }_k+E_{rep}\right]`$
This equation can be further simplified by making use of the Hellmann-Feynman feynman  theorem

$$𝐅_i=\underset{k}{}\mathrm{\Psi }_k\left|\text{}_{R_i}H\right|\mathrm{\Psi }_k_{R_i}E_{rep}.$$
(12)
The second term in the above equation is the short-ranged repulsive force. We should note that Pulay correction term does not play any role in any semi-empirical TBMD colombo . The reason is twofold. Within TBMD we directly compute the derivative of the TB Hamiltonian matrix element and the basis wavefunctions never appear explicitely, rather they are implicitely contained in the fitted matrix entries.

The motion of the atoms follow a classical behaviour and is governed by the Newton’s law :

$$m\frac{d^2𝐑_i}{dt^2}=𝐅_i,$$
(13)
where $`m`$ is the atomic mass.

For numerical simulation of Newtonian dynamics, we use the velocity Verlet molecular dynamics method swope  for updating the atomic coordinates, which is given by,

$$𝐑_i(t+\delta t)=𝐑_i(t)+𝐕_i(t)\delta t+\frac{1}{2m}𝐅_i(t)(\delta t)^2,$$
(14)
where the velocity $`𝐕_i`$ of the $`i`$th atom at $`t+\delta t`$ is calculated from $`𝐅_i`$ at $`t`$ and $`t+\delta t`$ as

$$𝐕_i(t+\delta t)=𝐕_i(t)+\frac{1}{2m}[𝐅_i(t)+𝐅_i(t+\delta t)]\delta t.$$
(15)
At this stage most authors carry out either dissipative dynamics or free dynamics with feedback methfessel . The reason for this is as follows : for numerical integration of Newton’s equations we have to choose a finite time-step $`\delta t`$. Ideally this should be as small as possible, but that would require an excessively long time for locating the global minimum. However, a large choice of $`\delta t`$ leads to unphysical heating up of the system, leading to instability. Dissipative dynamics has been suggested as a way of overcoming this. We add a small extra friction term carefully $`𝐅𝐅\gamma m\dot{𝐑}`$ menon4 . In the present calculation $`\gamma m=0.32`$ amu/psec, and the time step $`\delta t`$ is taken to be $`1`$ fsec and the total time for molecular dynamics simulation is $``$ 100 - 200 psec, depending upon the cluster size and initial cluster configuration with the several annealing schedule. Methfessel and Schilfgaarde methfessel  have also used an alternative technique of free dynamics with feedback to overcome the above difficulty.

The results of the molecular dynamics may depend sensitively on the starting configuration chosen. The final equilibrium configurations often correspond to local minima of the total energy surface and are metastable states. For the smaller clusters simulated annealing can lead to the global minimum. We have found the global minimum configurations of the smaller clusters by the simulated annealing technique. However, this is often not the case for the larger clusters. Recently more sophisticated techniques like the genetic algorithm has been proposed ga1 -ga4 . We have not tried this out in this communication, but propose this as an efficient technique for further work.

## III Results and Discussion

### III.1 Geometry optimization

We have applied this TBMD scheme to $`Cu_n`$ clusters for $`n55`$. Since the present scheme imposes no a priori symmetry restrictions, we can perform full optimization of cluster geometries. For small clusters ($`n9`$) we can able to perform a full configurational space search to determine the lowest-energy configuration. Here they serve as a test case for the calculation of larger clusters with $`n10`$. In Table 3 we present a detailed comparison of binding energy per atom, difference in binding energy $`\mathrm{}E`$ and average bond length $`r`$ for $`n9`$ with available experimental spasov  and ab initio kabir ; akeby ; massobrio  results. We found, in agreement with experimental ho  and theoretical massobrio ; calaminici ; akeby  results, very small copper clusters ($`Cu_3`$, $`Cu_4`$ and $`Cu_5`$) prefer planer structures. More detailed comparison, with experimental and ab initio results, can be found elsewhere kabir1 .

From the present results and detailed comparisons with various experimental ho ; spasov  and ab initio massobrio ; calaminici ; akeby ; kabir ; bauschlicher ; lammers ; wang  results available, we find reasonable agreement among this TBMD scheme and ab initio calculations for small clusters with $`n9`$ kabir1 , which allow us to continue the use of this TBMD scheme for larger clusters with $`n10`$. For larger clusters ($`10n55`$), due to increasing degrees of freedom with cluster size, a full configurational search is not possible with the available computational resources. Instead, led by the experimental and theoretical results on small clusters, we examined structures of various symmetries for each size. Most stable structures for $`n=1055`$ atom clusters are given in Fig.1.

In this regime, the structures predicted by this TB model are mainly based on icosahedron. The most stable structure of $`Cu_7`$ is a pentagonal bipyramid ($`D_{5h}`$ symmetry; see Table3), which is the building block for the larger clusters with $`n10`$. For $`Cu_{10}`$, we found a tricapped pentagonal bipyramid to be the most stable structure. Ground state structures of $`Cu_{11}`$ and $`Cu_{12}`$ are the uncompleted icosahedron with lack of one and two atoms respectively and a Jahn-Teller distorted first closed shell icosahedron is formed at $`Cu_{13}`$. For $`Cu_{13}`$, the fcc like cuboctahedron is less stable than the icosahedron by an energy $`0.05`$ eV per atom. In agreement Lammers and Borstel, on the basis of tight-binding linear muffin-tin orbital calculations, was also found the icosahedron to be the ground state of $`Cu_{13}`$, though the difference in energy between the icosahedron and the cuboctahedron was calculated to be only $`0.2`$ eV/atom lammers . The ground state structures for $`Cu_{14}`$, $`Cu_{15}`$, $`Cu_{16}`$, and $`Cu_{17}`$ are the 13- atom icosahedron plus one, two, three and four atoms respectively. A double icosahedron is formed for $`Cu_{19}`$ ($`D_{5h}`$ symmetry). This structure has two internal atoms, 12 six-coordinate atoms at either end and five eight-coordinate atoms around the waist of the cluster. Based on the structure for $`Cu_{19}`$, the stable $`Cu_{18}`$ cluster is a double icosahedron minus one of the six-coordinate atoms located at either end ($`C_{5v}`$ symmetry). Icosahedral growth continues for $`20n55`$ atom clusters. Polyicosahedral structure in the form of a “ triple icosahedron” ($`D_{3h}`$ symmetry; the structure can be viewed as three interpenetrating double icosahedra) is the most stable structure for $`Cu_{23}`$ cluster. The next closed shell polyicosahedra is found for $`Cu_{26}`$ cluster. Finally, the second closed shell icosahedron is formed for $`Cu_{55}`$ which is more stable than the closed cuboctahedral structure by an energy difference 6.27 eV. This can be explained in terms of their surface energy. The surface energy of the icosahedral structure is lower than that of the cuboctahedral structure, because the atoms on the surface of the icosahedron are five-coordinate compared to the four-coordinate atoms on the surface of the cuboctahedron. In our calculation, exception to the icosahedral growth is found at around $`Cu_{40}`$. The situation regarding geometrical structure in this size range is more complex. The structures for $`n=4044`$ atom clusters are oblate, decahedron like geometries. Return to the icosahedral structure is found at $`n=45`$. In the size range $`n=4044`$, the structural sequence is decahedron-icosahedron-cuboctahedron in decreasing order of stability, whereas in the region $`n=4555`$, the structures retain icosahedron-decahedron-cuboctahedron sequence.

This results are in agreement with the experimental study of Winter and co-workers winter , where they found a bare copper cluster mass spectrum recorded with ArF laser ionization shows a sudden decrease in the ion signal at $`Cu_{42}^+`$, and from this observation they argued that a change in geometrical structure might occur there, though they have not concluded about the nature of this geometrical change. They also found a dramatic decrease in water binding energy for $`Cu_{50}`$ and $`Cu_{51}`$, and concluded that this may represent a return to the icosahedral structure as the closed shell at $`Cu_{55}`$ is approached.

D’Agostino gda  confirms our prediction, who performed molecular dynamics using a tight-binding many-body potential and found that icosahedral structures are prevalent for clusters containing less than about 1500 atoms. Valkealahti and Manninen valkealahti , using effective medium theory, also found icosahedral structures are energetically more favourable than the cuboctahedral structures for sizes up to $`n2500`$ is consistent with our result: Fig.3 shows cuboctahedral structures are least stable among the three structures, icosahedron, decahedron and cuboctahedron. By contrast, Christensen and Jacobsen christensen1  predicted more fcc-like structures in the size range $`n=329`$, in their Monte Carlo simulation using an effective medium potential. But they correctly reproduced the “magic numbers” in that regime christensen1 ; christensen .

These results can be compared with the genetic algorithm study on copper clusters by Darby et al. darby , using Gupta potential. In agreement with the present study, Darby et al. found that most of the clusters in this regime adopt structures based on icosahedron. They also found exceptions to the icosahedral growth at around $`Cu_{40}`$, where the structures adopt decahedron like geometries (exact numbers are not available in the Ref.darby ). But the present study disagree with the genetic algorithm study in two points. Firstly, for $`25`$ atom cluster, they found a more disordered structure, while the present study predict it to be an icosahedron based structure which can be derived by removing one surface atom from the 26-atom polyicosahedron. Finally, they found an fcc-like truncated octahedral structure for $`Cu_{38}`$. Instead, the present study predict the icosahedron based structure to be the ground state, where this structure is energetically more favourable than the truncated octahedral structure by an energy $`\mathrm{}E=0.17`$ eV/atom. Although the genetic algorithm search for global minima is more efficient technique than molecular dynamics, use of the empirical atomistic potential is the main reason reason  for this kind of disagreement between Darby et al. and the present study.

### III.2 Binding energies and relative stabilities

The computed size dependence of the binding energy per atom for $`Cu_n`$ clusters with $`n=255`$ is depicted in Fig.2 (upper panel). Among all the isomeric geometries examined for a certain cluster size $`n`$, the highest cohesive energy has been considered for the Fig.2. The overall shape of the curve matches the anticipated trend: binding energy grows monotonically with increasing the cluster size. Inset of the Fig.2 (upper panel) shows the comparison of our calculated binding energy with the ab initio massobrio ; kabir  and experimental spasov  results. Experimentally the binding energies of the neutral clusters were derived from the dissociation energy data of anionic clusters from the TCID experiment spasov  and using electron affinities from the PES experiment ho . The inset figure shows that our calculated binding energies are in good agreement with those from DF-LDA massobrio  and our previous FP-LMTO kabir  calculations. However, our binding energies are systematically overestimated, by an energy $`0.53\pm 0.12`$ to $`0.79\pm 0.22`$, than the experimental binding energies. The LDA based ab initio calculations always over-estimate binding energies. This is a characteristic of the LDA. In the present study, TB parameters have been fitted to the ab initio LDA calculations for very small calculations kabir . It is not surprising therefore that the binding energies are over-estimated. In fact, the present results agree well with other LDA based calculations massobrio ; kabir , all of which overestimate the binding energy.

In the Fig.3, we compared binding energy per atom for cuboctahedral, decahedral and icosahedral structures for the clusters containing $`n=3055`$ atoms. Fig.3 shows most the clusters in this size range have icosahedral structures. However, a local structural change occured for $`n=4044`$, where the structures adopt decahedral structure rather than icosahedral one. Return to the icosahedral growth pattern is found at $`n=45`$ and continues up to 55-atom cluster. From the Fig.3 it is clear that among cuboctahedral, decahedral and icosahedral structures, cuboctahedral structures are least stable than the other two.

The second difference in the binding energy may be calculated as

$$\mathrm{}_2E(n)=E(n+1)+E(n1)2E(n),$$
(16)
where $`E(n)`$ represents the total energy for an $`n`$-atom cluster. $`\mathrm{}_2E(n)`$ represents the relative stability of an $`n`$-atom cluster with respect to its neighbors and can be directly compared to the experimental relative abundance : the peaks in $`\mathrm{}_2E(n)`$ coincide with the discontinuities in the mass spectra. These are plotted in the lower panel of Fig.2. We found three major characteristics in the Fig.2 (lower panel ). Firstly, even-odd (even $`>`$ odd) oscillation is found. This can be explained in terms of electron pairing in HOMOs. Even (odd) clusters have an even (odd) number of electrons and the HOMO is doubly (singly) occupied. The electron in a doubly occupied HOMO will feel a stronger effective core potential because the electron screening is weaker for the electrons in the same orbital than for inner shell electrons. Thus the binding energy of the valence electron with an even cluster is larger than of an odd one. This even-odd alternation is prominent up to $`n40`$. Secondly, due to electronic shell or subshell closing, we found particular high peak for $`n=8,18,20,34`$ and $`40`$. Unfortunately, the present study does not show any evidence of shell closing for $`Cu_2`$ in $`\mathrm{}_2E(n)`$. Finally, the even-odd alternation is reversed for $`n=1016`$ with maxima at $`Cu_{11}`$, $`Cu_{13}`$ and $`Cu_{15}`$, which manifests the geometrical effect and therefore there is no peak at $`n=14`$ due to electronic subshell closing. Simultaneous appearance of these three features in $`\mathrm{}_2E(n)`$ demonstrates the interplay between electronic and geometrical structure, which is in agreement with the experimental study of Winter et al. winter . They found both jellium-like electronic behaviour and icosahedral structure in copper clusters. In an experimental study of mass spectra of ionized copper clusters katakuse , substantial discontinuities in mass spectra at $`n=3,9,21,35,41`$ for cationic and $`n=7,19,33,39`$ for anionic clusters as well as dramatic even-odd alternation are found. From the sudden loss in the even-odd alternation at $`Cu_{42}`$ in the KrCl spectrum, Winter et al. argued about the possible geometrical change there. Therefore, we conclude in the section that sudden loss in the $`\mathrm{}_2E`$ vs $`n`$ plot (lower panel of Fig.2) is due the structural change in that regime.

Such kind of electronic effects can not be reproduced by empirical atomistic potentials. Darby et al. darby , using the Gupta potential, found significant peaks at $`n=`$ 7, 13, 19, 23 and 55 due to icosahedral (or polyicosahedral) geometries. In the present study, we have found a peak at $`n=13`$, but not at the other sizes found by them. However, the stable structures predicted by us are the same : the lowest energy structure of $`Cu_7`$ is a pentagonal bipyramid ($`D_{5h}`$ symmetry) ; for $`n=13`$ and $`55`$, the structure are the first and second closed icosahedral geometries respectively. Polyicosahedral structures are found for $`n=19`$ (double icosahedron) and $`n=23`$ (triple icosahedron) atom clusters. As the reason, the present study shows significant high peaks at $`Cu_8`$, $`Cu_{18}`$ and $`Cu_{20}`$ due to electronic shell closing effect and average peaks at $`Cu_{22}`$ and $`Cu_{24}`$ due to electron pairing effect. At these sizes, the electronic effects dominates over the geometrical effects and consequently the above peaks cannot observed by Darby et. al..

### III.3 HOMO-LUMO gap energies

Besides the second difference of the cluster binding energy, a sensitive quantity to probe the stability is the highest occupied-lowest unoccupied molecular level (HOMO-LUMO) gap energy. In the case of magic clusters shell or subshell closer manifests themselves in particularly large HOMO-LUMO gap, which was previously demonstrated experimentally ho ; pettiette . Calculated HOMO-LUMO gap energies are plotted in the Fig.4, where we observed even-odd alternation due to electron pairing effect and particularly large gap for $`n=2`$, $`8`$, $`18`$, $`20`$, $`34`$ and $`40`$ due to electronic shell and subshell closing. However, sudden loss of even-odd alternation is found around $`n40`$ due to the change in the geometrical structure in that region. Winter et al. winter  also found a sudden loss in even-odd alternation in the KrCl spectrum at $`Cu_{42}`$ and concluded this may coincide with any possible change in the geometrical structure there. In fact, Katakuse et al.  katakuse  observed identical behaviour in the mass spectra of sputtered copped and silver cluster ions : a dramatic loss of even-odd alternation at $`n=42`$, signifying a sudden change to a geometrical structure in which stability, and abundance, is less sensitive to electron pairing. Therefore, the sudden loss in the Fig.4 again confirms the structural change there. So, the present study correctly predicts the “magic numbers” in this regime correctly and confirms the experimental prediction : a geometrical change (icosahedron $``$ decahedron) is occurring around $`n40`$.

### III.4 Ionization potentials

Within the present TB scheme, we can get a ‘qualitative’ description of the ionization potentials with cluster size according to Koopmans’ theorem. This limitation arises mainly from the choice of the Slater-Koster (SK) TB parameters and the extent of their transferability ip , which may be improved by the proposed scaling scheme of Cohen, Mehl and Papaconstantopoulos cohen  . However, our aim is to get only a qualitative description of ionization potential with cluster size. Calculated ionization potentials are plotted in the Fig.5. In fact, we observed same pattern as it was in HOMO-LUMO gap energy vs cluster size : peaks at $`n=2`$, $`8`$, $`18`$, $`20`$, $`34`$, $`40`$ and even-odd alternation due to the same reasons discussed in the Sec. III.2. and Sec. III.3. Sudden loss in even-odd alternation around $`n40`$ is again confirmed from the Fig.5, which is due to the geometrical change there.

## IV Conclusion

Using tight-binding model we calculated ground state geometries, binding energies, second differences in binding energy, HOMO-LUMO gap energies and ionization potentials for copper clusters in the size range $`2n55`$. We have fitted the parameters of the present TB scheme from our previous ab inito calculations kabir . For small clusters $`n9`$, present results show good agreement with experimental ho ; spasov  and theoretical massobrio ; calaminici ; akeby ; kabir ; bauschlicher ; lammers ; wang  results, which allow us to go over the larger size range, $`10n55`$.

In the size range $`10n55`$ most of the clusters adopt icosahedral geometry which can be derived from the 13- atom icosahedron, the polyicosahedral 19-, 23-, and 26-atom clusters and 55-atom icosahedron, by adding or removing atoms. However, exceptions to the icosahedral growth is found around $`n40`$. A local geometrical transition is found for $`n=4044`$\- atom clusters. This is in agreement with the prediction of the two experimental studies by Katakuse et al.katakuse  and Winter et al.winter , where they predicted that a local geometrical transition may occur at $`n=42`$, though their results are not decisive about the nature of this geometrical change. Present results show that around $`n40`$ structures are changing from icosahedral to decahedral structure, where the structural sequence is decahedron-icosahedron-cuboctahedron in the decreasing order of stability. Return to the icosahedral growth is found at $`n=45`$, with the sequence icosahedron-decahedron-cuboctahedron in the decreasing order of stability.

As we have fitted the parameters of the present TBMD scheme from LDA based ab inito calculations kabir , calculated binding energies are in good agreement with the LDA based ab initio calculations but overestimates the same calculated from the TCID experiment spasov . In the present scheme, the “magic nimbers” ($`n=2`$, $`8`$, $`18`$, $`20`$, $`34`$ and $`40`$) due to electronic shell and subshell closing are correctly reproduced in the studied regime. Second difference of binding energy, HOMO-LUMO gap energy and ionization potential show even-odd oscillatory behaviour because of electron pairing in HOMOs in agreement with experiment. However, a sudden loss in even-odd alternation is found around $`n40`$ in the variation of second difference in binding energy, HOMO-LUMO gap energy and ionization potential with cluster size. This is in agreement with the experimental studies katakuse ; winter . We conclude this is due to the geometrical change (icosahedron $``$ decahedron) around there. Present results show that electronic structure can coexist with a fixed atomic packing.

Due to lower computational expense this TBMD scheme, with parameters fitted to first-principle calculation for the smaller clusters and with an environment correction, is a very efficient technique to study larger clusters, particularly with $`n10`$.

## Acknowledgments

This work is partially supported by the Centre for Catalytic Systems and Materials Engineering, University of Warwick, U. K. The authors are deeply grateful to S. Mukherjee and Luciano Colombo for helpful discussion.