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# Large transconductance oscillations in a single-well vertical Aharonov-Bohm interferometer

## Abstract

Aharonov-Bohm (AB) interference is reported for the first time in the conductance of a vertical nanostructure based on a single GaAs/AlGaAs quantum well (QW). The two lowest subbands of the well are spatially separated by the Hartree barrier originating from electronic repulsion in the modulation-doped QW and provide AB two-path geometry. Split-gates control the in-plane electronic momentum dispersion. In our system, we have clearly demonstrated AB interference in both electrostatic and magnetic modes. In the latter case the magnetic field was applied parallel to the QW plane, and perpendicular to the $`0.02\mu \mathrm{m}^2`$ AB loop. In the electrostatic mode of operation the single-QW scheme adopted led to large transconductance oscillations with relative amplitudes exceeding 30%. The relevance of the present design strategy for the implementation of coherent nanoelectronic devices is underlined.

PACS numbers: 73.23.-b

The pioneering work by Aharonov and Bohm had far-reaching fundamental implications as it pointed out the significance of potentials with respect to forces in quantum-mechanics. In their article, Aharonov and Bohm demonstrated that electrons propagating in the two arms of a ring-like structure experience a relative phase shift of $`e/\mathrm{}𝐀𝑑𝐥`$ (where $`𝐀`$ is the magnetic vector potential and the integral is performed along the ring) when a magnetic flux encircled by the ring is applied. This is true even if the classical Lorentz force is exactly zero along the electron path. A similar effect was predicted if one of the two arms was subjected to a change of its electrostatic potential, while keeping the electric field at zero by means of Faraday cages. If electrons injected and collected into/from the structure by means of leads propagate coherently, the phase shift was shown to manifest macroscopically in observable quantities such as conductivity. The latter was predicted to oscillate following cycles of constructive and destructive electronic interference.

Since its proposal, Aharonov-Bohm (AB) interference was demonstrated in several mesoscopic systems. The unprecedented advancement in semiconductor growth and nanofabrication technologies has opened the way to device applications of this effect. Indeed semiconductor devices based on electrostatic AB effect were proposed as building blocks for the development of coherent nanoelectronics. The advantages offered by quantum-interference devices with respect to conventional “classical” ones are very significant: a quantum interference transistor requires much smaller gate voltages compared to conventional FETs (some milliVolts compared to Volts) and this is expected to lead to higher transconductance and extremely small power dissipation .

AB effect relies on electronic phase coherence, however, and its observation in semiconductor heterostructures with marked and useful conductance oscillations demands high-quality materials and very careful design. Datta et al. pioneered the field and demonstrated for the first time magnetic AB oscillation in a GaAs/AlGaAs heterostructure with a contrast (defined as the ratio between the peak-to-peak amplitude and the mean value) smaller than 1%. Since then significant progresses were made in the quality of materials and in structure design, but even some more recent demonstrations of AB effect in semiconductor ring structures showed a contrast of the magnetic AB signal of only about 10% .

In light of successful applications of the AB effect to quantum devices, it is of crucial importance to achieve much higher contrasts and implement the electrostatic AB configuration. In this communication we propose and demonstrate a novel scheme for an AB interferometer based on a single modulation-doped wide GaAs quantum well. The two transport paths originate from the two lowest subbands of the well and take advantage of the $`\mathrm{\AA }`$ resolution achieved by epitaxial growth techniques. Spatial separation between the two electronic paths is given by the formation of a Hartree barrier in the well, lateral confinement is provided by surface gating.

The samples were fabricated from a high-mobility single-quantum-well GaAs/AlGaAs heterostructure containing a two-dimensional electron gas (2DEG) with a Hall mobility of $`510^6\mathrm{cm}^2\mathrm{V}^1\mathrm{s}^1`$ and a total carrier density of $`5.810^{11}\mathrm{cm}^2`$ at 4.2 K after illumination. Carriers were distributed in the two lowest subbands and Shubnikov-de Haas measurements yielded $`3.910^{11}\mathrm{cm}^2`$ electrons in the ground subband and $`1.710^{11}\mathrm{cm}^2`$ in the first-excited one. The 60 nm GaAs quantum well is located 75 nm below the surface and is embedded between Al0.25Ga0.75As barriers. Two $`\delta `$-doping layers are placed 35 nm (surface side) and 60 nm (substrate side) from the well. The choice of a wide single well instead of a double-quantum-well structure was motivated by the twofold need for spatially-separated transport paths and long coherence lengths. In this scheme, spatial separation is guaranteed by the Hartree barrier formed by Coulomb repulsion between carriers populating the modulation-doped quantum well (see inset in Fig. 1). At the same time, the absence of a central AlGaAs barrier reduces interface roughness scattering and alloy scattering.

One-dimensional leads are necessary to avoid smearing of the interference pattern in the electrostatic AB effect . Indeed, while for the magnetic AB effect phase shifts depend on the area enclosed by the two paths, for the electrostatic AB effect the shift depends on the transit time of electrons in the two arms of the ring . Consequently injection of an electron beam with no in-plane momentum dispersion is required for AB observation. To this end, an injector and a collector were realised on a Hall bar by patterning two long (5 $`\mu \mathrm{m}`$) split gates on the surface of the sample. (C, D and E, F in Fig. 1). The geometrical width of the gap between the electrodes is 0.5 $`\mu \mathrm{m}`$.) By appropriately biasing these gates it is possible to tune the number of modes propagating in the leads and, in the limit of zero temperature, in-plane momentum dispersion will be suppressed when a single mode is available for transport.

Given an estimated coherence length of about 1 $`\mu \mathrm{m}`$, electronic transport in the leads is expected to be diffusive. This is required in our scheme to avoid coherent reflections at their ends that could hinder the observation of the main interference effect. The injector and collector were individually characterised by measuring the low-temperature conductance of the sample versus the split-gate biases $`V_{\mathrm{CD}}`$ and $`V_{\mathrm{EF}}`$. None of them displayed clear signatures of conductance quantisation, confirming the diffusive nature of electron transport.

A third split gate (A, B) was used to define the ballistic one-dimensional region and tune the phase difference between propagating paths. Electrons can be reflected back or transmitted to the collector region depending on the interference being destructive or constructive. The split-gate length was chosen of 0.6 $`\mu \mathrm{m}`$, shorter than the estimated coherence length. Indeed the conductance of the device versus the bias ($`V_{\mathrm{AB}}`$) of the quantum point contact (QPC) defined by A and B displayed clearly quantised steps.

Fig. 2 shows the conductance of the device at different values of $`V_{\mathrm{AB}}`$ as a function of $`V_{\mathrm{CDEF}}=V_{\mathrm{CD}}=V_{\mathrm{EF}}`$. Sweeping $`V_{\mathrm{CDEF}}`$ from zero bias toward negative values, a one-dimensional channel is created as the 2DEG below the gates is depleted and then progressively narrowed until channel pinch-off at $`1`$ V. The value of the conductance in units of $`2e^2/h`$ at a fixed $`V_{\mathrm{AB}}`$ and at $`V_{\mathrm{CDEF}}=0`$ can be read as the number of propagating modes in the QPC. For $`3\mathrm{V}<V_{\mathrm{AB}}<1\mathrm{V}`$, corresponding to 2 to more than 3 modes in the QPC, very clear oscillations can be observed over a monotonically decreasing background as $`V_{\mathrm{CDEF}}`$ is swept below $`0.5\mathrm{V}`$. No oscillations could be seen when less than two modes are propagating in the QPC ($`V_{\mathrm{AB}}<3\mathrm{V}`$), that is when only a single path is available for transport.

Fig. 3 reports a set of oscillations obtained on one such device. Subtracting the contribution to the resistance due to the one-dimensional diffusive leads ($`10\mathrm{k}\mathrm{\Omega }`$) the contrast of the oscillations exceeds 30 %. To our knowledge, this value is the highest reported in the literature for semiconductor-heterostructure electrostatic AB rings and makes the present fabrication strategy of interest for device applications. Indeed the present structure does implement a possible quantum-interference transistor that yields a normalised transconductance $`dI_D/dV_G\times 1/I_D35V^1`$.

In order to understand the nature of the states (paths) involved in the interference processes it is necessary to distinguish between different situations. For sake of simplicity, we focus on the case of two propagating modes in the QPC. This configuration can occur in two different ways: i) only the first two transverse modes originating from the lower quantum-well subband are below the Fermi level and all modes originating from the upper subband are depleted; ii) electrons occupy the first transverse mode of each one of the two quantum-well subbands. To understand which of these possibilities is of interest here, we measured the conductance of our device at appropriately chosen gate biases as a function of an in-plane magnetic field perpendicular to the current. The magnetic field will couple to the loop formed by the two propagating paths and lead to magnetic AB oscillations only when configuration ii) is realised. As reported in Fig. 4, very clear conductance oscillations can be seen as a function of magnetic field. Consistently with the results reported above, interference effects occur only when $`V_{\mathrm{CDEF}}`$ is swept below $`0.5\mathrm{V}`$. Again, no oscillations can be resolved when a single mode is accessible in the QPC. The period of AB oscillations is given by $`\mathrm{\Delta }B=h/eS`$, where $`S=Ld0.02\mu \mathrm{m}^2`$ is the area enclosed by the two paths, $`d`$ is the center-to-center distance between the channels and $`L`$ is the length of the two channels. For our sample we estimate $`L0.6\mu \mathrm{m}`$ from the geometrical width of the QPC and $`d35\mathrm{nm}`$, obtained from a self-consistent calculation of the two subband wavefunctions. These values give a theoretical period $`\mathrm{\Delta }`$B $`0.19\mathrm{T}`$, in good agreement with the values of $`0.2\mathrm{T}`$ and $`0.26\mathrm{T}`$ measured from the data with $`V_{\mathrm{CDEF}}=0.5\mathrm{V}`$ and $`V_{\mathrm{CDEF}}=1.2\mathrm{V}`$ respectively (in both cases $`V_{\mathrm{AB}}=2.5\mathrm{V}`$). The greater period measured in the latter case is linked to the increased wavefunction confinement and consequent reduction of AB loop area.

In summary, we have demonstrated a novel scheme leading to very high-contrast Aharonov Bohm interference driven both by an electric and a magnetic field in a high-mobility heterostructure. The analysis of the results allowed to unambiguously identify the states involved in the process. The present structure does implement a quantum interference transistor device that in its present configuration leads to a normalised transconductance analogous to that of classical devices.

This work was funded in part by the British Council and CRUI within the British-Italian collaboration scheme. The work at Cambridge was supported by the UK EPSRC. C. T. L. is grateful for the support from the NSC, Taiwan. Molecular beam epitaxial growth at the Walter Schottky Institut (TU Munchen) is supported by the Deutsche Forschungsgemeinschaft via SFB 348 and the Bundesministerium für Bildung und Forschung under contract 01 BM 630/1. We would like to thank Spiros Gardelis for his help in sample preparation.


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# Balanced Branching in Transcription Termination

## I Introduction

The branching ratio of the termination process in gene transcription is balanced. In the case most thoroughly studied, $`\rho `$-independent termination in procaryotes, conventional gel experiments performed in vitro find a fraction $`P`$ of elongating RNA polymerase reading through the termination sequence with $`|\mathrm{ln}(1/P1)|<4`$ essentially always, even though $`P`$ is different for different terminators and can be made to exhibit order-1 changes by perturbing the environment. This effect is astonishing from the standpoint of microscopic physics because a stochastic decision to read through or not requires a competition of transition rates - quantities of inverse time - that must be nearly equal for the branching to be balanced. RNA polymerase, however, is more the size of a glass simulation than a small molecule and thus possesses a broad spectrum of natural time scales spanning many decades. Without some physical reason for a particular scale to be preferred, rate competition ought to have been severely unbalanced, meaning that one event occurs essentially always and the other never. Balanced branching in termination has been implicated in transcription regulation in a few cases,  but its broader significance, especially its robustness, is still a mystery.

In this paper we examine the experimental facts relevant to the physical nature of termination with the goal of determining what, if any, principle selects the time scale for stochastic rate balance. Our conclusion is both surprising and unsettling. We find no evidence for such a principle, but glaring weaknesses in the case for stochasticity and a large body of unexplained experimental results pointing to a termination decision that is partially deterministic. In light of the inaccessability of systems this large to ab-initio computation we conclude that transcription termination is a fundamentally unsolved problem in mesoscopic physics and an ideal target for the emerging techniques of nanoscience.

## II Termination Efficiency

The simplest termination sequences are the $`\rho `$-independent terminators of procaryotes, which are capable of causing polymerase to terminate in vitro in the absence of the $`\rho `$ protein factor. A representative sampling of these is reproduced in Table I. This differs from lists that have appeared in the literature before  by having been rechecked against the fully-sequenced genome  and expunged of “theoretical” terminators identified only by computer search. They conform for the most part to the motif of a palindrome of typically 10 base pairs followed by a short poly-T stretch, although there is tremendous variety in the length and composition of the palindrome, variation in the length of the poly-T stretch, and occasional extension of the palindrome to include the poly-T stretch. This enormous variability contrasts with the simplicity of stop codons, which terminate protein synthesis by ribosomes and have no other function.

$`\rho `$-independent terminators are characterized by “efficiencies”, i.e., the fraction of assayed transcripts that terminate. These rarely take on extreme values close to 1 or 0 when measured in vitro. In cases where a measurement in vivo exists as well the latter is usually larger  and is occasionally unmeasurably close to 1. Balanced termination efficiency is commonly observed in vivo as well, however. Table II shows results from a particularly careful study  in vitro in which termination probabilities in E. coli for wild-type terminators, mutant terminators, phage terminators,  and terminators from S. Boydii were measured under identical conditions. Despite the great variety of these sequences the termination efficiency runs only

\[

\]

from 2% to 88%. Many other researchers report similar values for terminators in E. coli and other bacteria,  including artificially altered terminators.

The results in Tables III and IV show balanced termination for modified versions of the phage terminator tR2  and for mutant polymerase.  This also makes order-1 changes to the efficiencies themselves. Similar effects were reported by other researchers  with different mutant polymerases. Modifications up to 20 base pairs upstream and downstream of the terminator cause large changes to the efficiency without causing it to unbalance.  Thus balanced termination efficiency is the norm rather than the exception.

## III Large Molecules and Glasses

Large systems are qualitatively different from small ones.  The specific heat of all non-crystalline matter in macroscopic quantities - including biological matter - is proportional to $`T`$ at low temperatures.  This behavior is fundamentally incompatible with the linear vibration of the atoms around sites, and is caused by collective quantum tunneling of atoms between energetically equivalent “frustrated” configurations.  It contrasts sharply with the $`T^3`$ behavior of crystals with small unit cells. Glasses also exhibit stretched-exponential time dependence in response to perturbations, i.e., of the form $`\mathrm{exp}(At^\beta )`$ with $`\beta <1`$, indicating a broad spectrum of decay rates rather than just one. They also exhibit memory effects, such as “remanence” in spin glasses  or the well-known failure of ordinary silica to crystallize without annealing. This behavior is universal and robust. All non-crystalline macroscopic matter exhibits hysteresis, metastability, a broad spectrum of relaxation times, and memory.

How large a system must be before it can exhibit such behavior is not known, as the relevant experiments are difficult to perform except on macroscopic samples, but there are many indications that even medium-sized proteins have glass-like properties. Crystals of myoglobin, a protein with a molecular weight of only 17,000, have linear specific heats at low temperatures  and exhibit stretched-exponential response to photodissociation pulses.  Denatured proteins refold on a variety of time scales ranging from nanoseconds to seconds,  and amino acids sequences chosen at random will not fold at all.  Permanent misfolding of proteins with molecular weights of only 30,000 has been implicated in prion diseases.  Many enzymes exhibit hysteresis in their

catalytic rates.  The activity of cholesterol oxidase of Brevibacterium sp., a protein with molecular weight 53,000, was recently shown by fluorescence correlation techniques to have a memory effect persisting about 1 second under normal conditions at room temperature.  Other notable examples include wheat germ hexokinase (mol. wt. 50,000 ) with a half-life of 2 minutes,  rat liver glucokinase (mol. wt. 52,000 ) at 1 minute,  and yeast hexokinase (mol. wt. 50,000) at 1-2 minutes.  Thus RNA polymerase complexes, which have a molecular weight of 379,000 and are comparable in size to the largest computer simulations of glasses ever performed, are good candidates for systems that exhibit glassy behavior.

Glassiness in enzymes is not always easy to observe. The mnemonic effect in yeast hexokinase occurs when it is preincubated with MgATP and free Mg2+ and the reaction is started with glucose, or preincubated with glucose and free Mg2+ and started with MgATP, but not if the enzyme is preincubated with glucose and metal-free ATP and then started with Mg2+.  Mnemonic behavior can be destroyed by “desensitizing” the enzyme with contaminants.  Time scales can depend on enzyme, substrate, product, activator and effector ligand concentrations as well as pH, buffers, and temperature.  Before hysteresis and memory effects were recognized, early investigators generally adjusted such reaction conditions until the “improper” behavior was eliminated.

## IV Polymerase States

While the size of RNA polymerase makes it plausible to expect glassy behavior on purely theoretical grounds, several direct lines of evidence indicate that the enzyme exhibits a spectrum of multiconformational, mnemonic and hysteretic behavior:

1. Polymerase has a catalytic mode distinct from RNA synthesis, as it can cleave the RNA transcript through hydrolysis (rather than pyrophosphorolysis, the reverse reaction of RNA synthesis),  with the cleavage reaction requiring Mg2+,  being template-dependent,  changing the polymerase footprint size,  and stimulated either by GreA and GreB proteins  or by high pH (8.5-10.0).  The last effect was discovered serendipitously, going unobserved for decades because assay conditions were being optimized to maximize elongation rates, which occur at lower pH values (7.8-8.2 ).
2. RNA polymerase mobilities in non-denaturing electrophoresis gels show significant and discontinuous variance while bearing nearly identical transcripts or identical length transcripts with different sequences.  These mobility variances are still observed if the RNA transcript is first removed by ribonuclease digestion.
3. RNA polymerase ternary complexes vary greatly in their stability and mode of binding to DNA (ionic or non-ionic) in a template-dependent manner. Some complexes are stable against very high salt concentrations (\[K+\] = 1 M), while others (specifically those proximal to an upstream palindrome sequence) are salt-sensitive (completely dissociating in concentrations as low as 20 mM K+). However, the salt-sensitive complexes are stabilized by millimolar concentrations of Mg2+.
4. The size of the RNA polymerase footprint on the DNA template measured by ribonuclease digestion is significantly altered even at adjacent template positions, suggesting that the enzyme assumes different conformations during elongation.
5. Guanosine tetraphosphate (ppGpp) inhibits the rate of elongation on natural DNA templates but not on synthetic dinucleotide polymer templates, and does not inhibit elongation by competing with NTP binding, but by enhancing pausing. It must therefore bind to polymerase and modify its behavior at an unrelated regulatory site in an allosteric manner, rather than interfering with the substrate binding site.
6. The stability of a stalled elongation complex depends on whether the polymerase arrives at the stall site via synthesis or pyrophosphorolysis.
7. Termination efficiencies are affected by transcribed upstream sequences and untranscribed downstream sequences adjacent to the terminator.
8. Stalling elongating polymerase complexes (via nucleotide starvation) and then restarting them by nucleotide addition perturbs pausing patterns 50-60 base pairs downstream.
9. An elongating polymerase’s Michaelis constants $`K_S`$ for NTPs vary over 500-fold for different DNA template positions,  and for different templates,  although these effects are not observed for synthetic dinucleotide polymer templates.
10. The rate of misincorporation at a single site for which the correct NTP is absent is significantly different before and after isolation of ternary complexes.
11. Stalled polymerase gradually “arrests” (i.e., is incapable of elongating when supplied with NTPs), with the approximate half-time for arrest estimated at 5 minutes  and 10 minutes  for different DNA templates. The polymerase can continue elongating if reactivated by pyrophosphorolysis.
12. Even after undergoing arrest, crosslinking experiments show that the internal structure of polymerase gradually changes over the course of the next hour.
13. Observations of single elongating RNA polymerase molecules show that it has two elongation modes with different intrinsic transcription rates and propensities to pause and arrest.

The possibility of metastability - through shape memory or the conditional attachment of factors - is directly relevant to the rate-balance conundrum because it provides a simple alternative to balanced stochastic branching that requires no physical miracles. If, for example, the polymerase possessed a small number of metastable configurational states and terminated deterministically depending on which state it was in, then balanced branching would be a simple, automatic consequence of scrambling the state populations.

## V Thermal Activation

The idea that polymerase memory is potentially relevant to expression regulation is not new.  It is implicit in the work of Goliger et al  and Telesnitsky and Chamberlin  and even explicitly speculated by the latter in print. However, because of the experimental evidence supporting the stochastic model of termination  and the widespread belief - unjustified, in our view - that proteins equilibrate rapidly, this suggestion generated little enthusiasm. A key experiment supporting the stochastic model by Wilson and von Hippel  is both historically important and typical, so it is appropriate that we consider it carefully.

Wilson and von Hippel promoted and stalled RNA polymerase 8 base pairs upstream of the tR2 terminator hairpin of phage $`\lambda `$ in vitro, thermally equilibrated at temperature $`T`$, and then launched it forward by adding NTP. The results are reproduced in Fig. 1a. Termination occurred at sites 7, 8, and 9 base pairs downstream of the beginning of the poly-T stretch (cf. Table II) with probabilities $`P_7=N_7/N`$, $`P_8=N_8/N`$ and $`P_9=N_9/N`$. The data were originally reported as a semilogarithmic plot of $`1/\widehat{P}1`$ against temperature, where $`\widehat{P}_7=N_7/N`$, $`\widehat{P}_8=N_8/(NN_7)`$ and $`\widehat{P}_9=N_9/(NN_7N_8)`$. They concluded that all three branching probabilities $`\widehat{P}`$ were thermally activated and had distinctly different activation energies. However, it is clear from Fig. 1a that this conclusion is false. The three probabilities $`P`$ are essentially the same function and are well characterized by the sum $`P=P_7+P_8+P_9`$, also plotted in Fig. 1a. This is shown more explicitly in Fig. 1b, where the ratios $`P_7/P`$, $`P_8/P`$, and $`P_9/P`$ are plotted against temperature. The flatness of these curves shows that the branching ratios among the three sites are essentially constant and independent of temperature within the error bars of the experiment. Note that these fractions are also all of order 1. Thus the alleged spread in activation energies was an artifact of the plotting procedure.

Let us now consider the temperature dependence. It may be seen from Fig. 1a that $`P`$ saturates to 1 at 80 C, the temperature at which Wilson and von Hippel

report that the polymerase “will not elongate”, i.e., has stopped working properly. This suggests that the effect has something to do with the overall mechanical integrity of the enzyme rather than the termination process alone. Guided by this observation we note that the activated behavior identified by Wilson and von Hippel is actually the formula for conventional monomolecular chemical equilibrium. The probability for a particle of mass $`M`$ with a binding energy of $`E_0`$ to be ionized off the polymerase is

$$P=\frac{1}{1+Ze^{E_0/k_BT}n\lambda _{th}^3}(\lambda _{th}=\sqrt{\frac{2\pi \mathrm{}^2}{Mk_BT}}),$$
(1)
where $`n`$ is the concentration of this component and $`Z`$ is the change to the internal partition function that results from binding. If one makes the approximation that $`\lambda _{th}`$ is a slowly-varying function of temperature and can thus be taken to be constant then this reduces to the formula with which Wilson and von Hippel fit their data.  That it works may be seen in Fig. 1c, where we plot the total termination probability from experiment against Eq. (1) with $`E_0=0.7eV`$ and $`Z`$ adjusted to match experiment at T = 30 C. Thus reinterpreting this effect as an ionization equilibrium, we may account for the high-temperature intercept and weak temperature dependence seen in Fig. 1b in the following way: In addition to the ionization state the polymerase possesses an internal configurational memory with a number of states of order 10. These code for termination at sites 7, 8 or 9. In the equilibration step, the polymerase molecules come to thermal equilibrium and a fraction $`P`$ of them become ionized. All of these terminate at one of the three sites when launched. The rest read through.

A candidate for the ionizable component is an Mg2+ ion. In their studies of the effects of ion concentrations on termination efficiency, Reynolds et al  discovered that Mg2+ has the strange and unique effect of increasing termination efficiency to 100% for all terminators studied when reduced below 1 mM. The Mg2+ concentration in the experiments shown in Fig. 1d was 10 mM.  Extrapolating at T = 30 C  using Eq. (1) we obtain, with no adjustable parameters, the fit to the \[MgCl2\] dependence found by Reynolds et al shown in Fig. 1d. The quality of this fit suggests that Mg2+ has a special function in regulating transcription, and that the temperature dependence in Fig. 1a is simply a thermal binding relation for this ion. This is corroborated by the recent structural studies of Zhang et al,  who report that polymerase crystallized out of 10 mM solution of MgCl2 has a Mg2+ ion bound at what appears to be the catalytic site of the enzyme.

There is evidence for more termination channels other than the ionization of Mg2+. In Fig. 2 we reproduce results of Reynolds et al  showing that terminator efficiencies tend to saturate at large Mg2+ concentration to values other than zero. The saturation values are balanced, and there is an evident tendency of them to cluster. Both effects are consistent with the polymerase executing an instruction at the terminator to read through conditionally, even when the ionizable component is bound, if its memory is appropriately set. There is obviously not

enough data here to draw such a conclusion, however. We note that Reynolds et al  also found order-1 effects on the termination efficiency from Cl- and K+, although with the opposite sign. The function of these ions is not yet known.

## VI Antitermination

What experiments can detect internal memory? In general, one would look for cases in which polymerase acts differently under apparently identical conditions, suggesting an internal control mechanism of some kind. Such thinking motivates the following hypothetical experiment: one constructs a template with promoter $`P`$ followed by two identical terminators and flanking DNA sequences in succession. If termination is stochastic, then the branching ratio at T2 will be the same as that at T1. If termination is deterministic and hysteretic, then the branching ratios will be different, depending on details. A passive termination at T1 would result in no termination at T2, since the polymerase that reads through has been “polarized”, i.e., selected for the memory setting that codes for read-through. An active termination at T1 would reprogram the memory there and cause a termination probability at T2 different from that of T1 but not necessarily zero. Variations of this design, e.g., adding more terminators, combining different terminators, changing their order, etc., could, in principle, answer more sophisticated questions, such as whether and how polymerase is reprogrammed in active read-through and whether non-equilibrium effects are important.

A few such experiments have already been performed on DNA templates containing antiterminators (sequences upstream of terminators that reduce termination efficiencies) and are thus less general than one would like, but they strongly support the idea of polymerase memory. There is indirect evidence in the case of N-antitermina-tion of phage $`\lambda `$, the case most studied, that the memory is a physical attachment of the transcribed mRNA to the

polymerase to form a loop.  There is also evidence that it is not true generally.

In 1989 Telesnitsky and Chamberlin  reported memory effects associated with the lac antiterminator found just downstream of the Ptac promoter in E. coli. Their key result is reproduced in Table V. Insertion of lac 353 nucleotides upstream of the terminator makes different order-1 modifications to the termination efficiences of T7Te phage and trp a. The antiterminator contains a palindrome, and the antitermination effect is sensitive to modifications of the downstream 15-base-pair sequence. 3 copies of T7Te placed in tandem downstream of lac showed that the antitermination effect is partially remembered through multiple terminators: the efficiencies were 44%, 60%, and 90%, but without the antiterminator they were 90%, $`>`$90%, and $`>`$90%.

In another experiment in vitro reported in 1989, Goliger et al  found that the E. coli terminator rpoC t and phage terminators oop t and t82 were strongly antiterminated by a sequence they constructed accidentally. Their key result is reproduced in Table VI. A phage 82 promoter was fused onto a sequence containing either rpoC t alone or oop t

and rpoC t in tandem using the EcoRI linker sequence GGAATTC. This resulted in unexpected antitermination in vitro of both terminators, but of different sizes that depended sensitively on the insertion point. The read-through effects in the tandem experiments were unfortunately poorly documented. One can see from Table V that the phage terminator responded more strongly in this experiment than did rpoC t. However, the reverse was the case in another experiment in which the antiterminator was a portion of the 6S RNA gene downstream of a phage $`\lambda `$ pR promoter, and in which factor NusA was present. As a control, this latter experiment was rerun with the phage terminator t82, which terminated at greater than 98% in all cases, seemingly immune to antitermination.

King et al  reported in 1996 that the putL and putR antitermination sequences of the Hong Kong phage HK022,  shown in Table VII, caused downstream readthrough of a triple terminator consisting of tR from phage $`\lambda `$ followed by the strong E. coli ribosome operon terminators rrn B t1 and rrn B t2. This effect was sensitive to the choice of promoter. When putL was inserted between the Ptac promoter and the triple terminator 284 nucleotides downstream and studied in vivo the termination probability was 50%. Substituting the phage $`\lambda `$ PL promoter for Ptac under the same conditions resulted in complete readthrough (though with wide error bars). When this experiment was repeated in vitro the antitermination effect was found to be smaller and to persist through all three terminators. The read-through probabilities at tR were 34% and 31% for promotion by PL and Ptac, respectively, but 57% and 27% for rrnB t1 and 76% and 40% for rrnB t2. This result is incompatible with statistical termination, for both the antitermination effect itself and the changes resulting from switching promoters are order-1 effects that do not add. They also reported that reduced Mg2+ concentration destroys the antitermination effect.

## VII Conclusion

In summary we find that the theory of stochastic termination, which requires natural selection to engineer a physical miracle of balanced rates, is flawed, but that there is ample evidence of a sophisticated and as-yet poorly understood regulatory system in RNA polymerase involving hysteresis, metastability, and long-term configurational memory, all robust phenomena in inanimate matter. On this basis we predict that branching ratios of

identical terminators in series will differ by order-1 amounts very generally - specifically in the absence of looping. We propose that the confusion surrounding the existence of polymerase memory is symptomatic of the larger problem that measurement of physical activity on the length and time scales appropriate to life has thus far been impossible, and that overcoming this problem should be one of the high-priority goals of modern nanoscience.

This work was supported primarily by NASA Collaborative Agreement NCC 2-794. SL would like to acknowledge informative discussions with Brian Ring. RBL wishes to express special thanks to the organizers of the Keystone conferences, particularly R. Craig, for encouraging interdisciplinary science. We also wish to thank the Institute for Complex Adaptive Matter at Los Alamos, the Brown-Botstein group at Stanford for numerous stimulating discussions, and H. Frauenfelder, J. W. Roberts, D. Botstein and M. J. Chamberlin for a critical reading of the manuscript.


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# Symmetry crossover and excitation thresholds at the neutral-ionic transition of the modified Hubbard model

## I Introduction

McConnell and coworkers explained the sharp separation of organic charge transfer (CT) complexes into diamagnetic and paramagnetic by proposing that weak $`\pi `$-donors (D) and acceptors (A) form neutral complexes of molecules, while strong donors and acceptors crystallize as ion radicals D+ and A-. These planar conjugated systems form one-dimensional structures, either as mixed …DADA… stacks in CT complexes or as segregated stacks in ion-radical salts . The simplest approximation for a crossover between DA and D+A- ground states is $`M=E_IE_A`$, where $`M`$ is the Madelung energy, $`E_I`$ is the ionization potential of the donor and $`E_A`$ is the electron affinity of the acceptor. Although $`M`$ is inherently long ranged, the systems are quasi one-dimensional by virtue of $`\pi `$-overlap restricted to stacks. Strebel and Soos  introduced the modified Hubbard model with transfer integral $`t=DA|H|D^+A^{}`$ for CT complexes and studied the crossover in the random phase approximation. Finite $`t`$ leads to mixing and to partial ionicity Dρ+Aρ- in the ground state (GS), with $`\mathrm{\Delta }\rho <1`$ at the crossover. The modified Hubbard model, Eq. (1) below, has proved to be extremely rich and widely applicable. It describes any valence transition, is a special case of important solid-state models, and provides the starting point for electron-phonon (e-ph) coupling. Its scope is still growing and attracting new theoretical and computational approaches to the crossover region, $`ME_IE_A`$. We present in this paper exact solutions of finite-size systems, including low-lying excitations.

The neutral-ionic transition (NIT) originates with the TTF-CA complex studied by Torrance and coworkers , with D = tetrathiafulvalene and A = chloranil. TTF-CA is neutral at room temperature, with $`\rho `$ 0.3, and has a transition at T $``$ 81K to an ionic state with $`\rho `$ 0.7 that, moreover, is dimerized. The uniform TTF-CA spacing above 81K becomes alternating ($`\mathrm{}t_1,t_2\mathrm{}`$) in the ionic phase, and partial ionicity is determined spectroscopically . The structural change shows the fundamental role of lattice phonons and the Peierls instability of the paramagnetic phase. The alternating phase is potentially ferroelectric and the system may be metallic at the NIT. Such features are common to ferromagnetic oxides, and in this context they have recently been discussed  in terms of the modified Hubbard model. The interplay of electron-electron (e-e) and e-ph interactions can generate either continuous or discontinuous ionicity changes. Long-range Coulomb interactions can generate  discontinuous $`\rho `$ variations at the NIT as well as strongly affect  the dimerization instability.

Rice  pointed out the strong infrared activity of totally symmetric molecular vibrations through coupling to charge fluctuations. These on-site (Holstein) phonons also participate in the NIT. They condense at the transition and produce discontinuous $`\rho `$ variations above a critical coupling strength . Electron-molecular-vibration coupling provides the basis for the spectroscopic determination of the ionicity, $`\rho `$, of the Dρ+Aρ- GS as well as of the local symmetry, making vibrational spectroscopy an useful tool to follow charge and structural phase transitions . Joint theoretical and experimental analysis of electronic and vibrational spectra  allowed for a systematic characterization of several salts .

The modified Hubbard model adds site energies $`\pm \mathrm{\Delta }`$ to a Hubbard chain with uniform spacing,

$$H_0(t,\mathrm{\Delta },U)=\underset{i,\sigma }{}\left\{t\left(a_{i,\sigma }^+a_{i+1,\sigma }+a_{i+1,\sigma }^+a_{i,\sigma }\right)\mathrm{\Delta }(1)^ia_{i,\sigma }^+a_{i,\sigma }\right\}+\underset{i}{}Ua_{i,\alpha }^+a_{i,\beta }^+a_{i,\beta }a_{i,\alpha }$$
(1)
D and A are at odd and even $`i`$, respectively, in the context of CT complexes, and $`t>0`$, $`\mathrm{\Delta }`$ 0 can be taken without loss of generality. The half-filled case, with one electron per site, is by far the most important. We consider $`H_0`$ at this filling for uniform $`t`$ and equal $`U`$ 0 for donors and acceptors. The electron density on D sites is related to the GS energy,

$$n_D1=\frac{1}{N}\frac{E_0(t,\mathrm{\Delta },U)}{\mathrm{\Delta }}$$
(2)
The ground states of extended systems are not known exactly for $`\mathrm{\Delta }0`$. Approximate solutions beyond mean field have been proposed along several lines: exact diagonalization , quantum Monte Carlo , renormalization group methods, and continuum models . There is broad agreement as well as open or disputed points mentioned below.

Hubbard models are readily generalized and provide a unified approach to quantum cell models that need not be low-dimensional. In the context of Eq. (1), we note that $`\mathrm{\Delta }`$ can incorporate the Madelung energy in a mean-field approximation  or coupling to Holstein phonons in the adiabatic approximation . In either case, the effective $`\mathrm{\Delta }`$ depends on the GS ionicity and the NIT becomes discontinuous above a critical coupling. The model is then nonlinear and has wider applications to susceptibilities . At $`\mathrm{\Delta }=0`$, if $`t`$ is linearly expanded around the equilibrium bond-length, we get a Peierls-Hubbard model , and a direct connection to models for ion-radical salts such as TTF-TCNQ with segregated stacks. Alternating transfer integrals $`t(1\pm \delta )`$ are found on the ionic side  in many segregated stacks and in conjugated polymers . Theoretical interest in $`H_0(t,\mathrm{\Delta },U)`$ and its variants lies in the interplay of e-e and e-ph interactions and their role in the structural instabilities of 1-D materials, broadly defined .

The $`t=0`$ GS of the Hamiltonian in Eq. (1) is sketched in Fig. 1 to illustrate some basic features. The electrons are paired on D (odd) sites for $`\mathrm{\Delta }>U/2`$, paired on A (even) sites for $`\mathrm{\Delta }<U/2`$, and singly occupy all sites in between; covalent states have $`n_i=1`$ at all $`i`$ and spin degeneracy of $`2^N`$. The valence transitions at $`U=\pm 2\mathrm{\Delta }`$ for $`U>0`$ transfer one electron in the GS and $`\rho =2n_D`$ changes discontinuously. Since the paired GS in Fig. 1 are nondegenerate, we expect finite gaps for spin, optical and charge carrying excitations. The covalent GS, on the other hand, has vanishing spin gaps.

$`H_0(t,\mathrm{\Delta },U)`$ with finite $`t`$ is a one-dimensional metal at $`\mathrm{\Delta }=U=0`$, a band insulator for $`\mathrm{\Delta }>0`$, $`U=0`$, and a Hubbard model for $`\mathrm{\Delta }=0`$, $`U>0`$. Finite $`t`$ leads to continuous $`n_D`$ at the NIT when $`\mathrm{\Delta }`$ is not a function of $`n_D`$. Although the ionicity is continuous, the NIT between band and Mott insulators is a true quantum phase transition at T=0K as signaled by the closing of triplet  and singlet  gaps and by the unconditional instability  to dimerization on the covalent side. The nature of the transition between two insulators has revived interest in the modified Hubbard model in connection with localization and conductivity in correlated systems . Strong charge fluctuations induced by lattice motion  and related structural instabilities  have been rediscovered and underlined. Finite $`t`$ generates correlated states of the Hamiltonian in Eq. (1) that differ fundamentally from the $`t=0`$ limit. In spite of sustained research , no definitive picture has emerged for the T=0K phase diagram of the simple model in Eq. (1).

We present in this paper exact solutions of $`H_0(t,\mathrm{\Delta },U)`$ for finite $`N`$ using valence bond (VB) methods  that were originally developed  for CT complexes. Total spin $`S`$ is conserved in all versions of Eq. (1). VB diagrams with specified pairing of sites with $`n_i=1`$ form a large but complete basis for any $`N`$. The scope of finite-$`N`$ results is decisively extended by using both periodic and antiperiodic boundary conditions and the symmetries of $`H_0`$. The oligomers in Section 2 reach $`N`$ = 16 in the full basis or $`N`$ = 22 in a restricted basis without D2+ or A2- sites, compared to $`N`$ 10 in previous studies. Exact excitations near the NIT are related in Section 3 to the opening of gaps and interpreted as due to localization on the paired side. The GS is metallic at the NIT according to the charge gap and charge stiffness. The NIT marks the boundary between a localized GS for $`\mathrm{\Delta }>>U`$, and a delocalized GS with vanishing excitation energies as in Hubbard models at $`\mathrm{\Delta }=0`$. We shall briefly mention the role of e-ph coupling and intersite e-e interactions, but defer detailed analysis to subsequent publications.

## II  Symmetry crossover and charge density

We consider GS properties of $`H_0(t,\mathrm{\Delta },U)`$ at half filling, one electron per site, and uniform $`t`$ = 1. General solutions of the Hamiltonian in Eq. (1) are restricted to finite $`N`$, where eigenstates and energies are accessible. Periodic boundary conditions (PBC) are readily applied to noninteracting ($`U=0`$) systems whose GS energy is

$$\frac{E_0(\mathrm{\Delta },0)}{N}=\frac{1}{N}\underset{kfilled}{}2(\mathrm{\Delta }^2+4\mathrm{cos}^2k)^{1/2}\frac{2}{\pi }(\mathrm{\Delta }^2+4)^{1/2}E(q)$$
(3)
The expression for the infinite chain is shown in Fig. 1; $`E(q)`$ is the complete elliptic integral of the second kind, with $`q^2=4/(\mathrm{\Delta }^2+4)`$. From Eq. (2) the GS electronic density on D is:

$$n_D(\mathrm{\Delta },0)1=\frac{2\mathrm{\Delta }K(q)}{\pi (4+\mathrm{\Delta }^2)^{1/2}}$$
(4)
where $`K`$ is the complete elliptic integral of the first kind. The divergence of $`n_D/\mathrm{\Delta }`$ at $`\mathrm{\Delta }=0`$ signals an electronic instability. The behavior of finite rings is different and shows 4n, 4n+2 effects. The wavevector is $`k=0,\pm 2\pi /N,\pm 4\pi /N,\mathrm{}\pi `$. We have energies $`\pm \mathrm{\Delta }`$ at $`k=\pi /2`$ when $`N`$ = 4n and two electrons for these orbitals. The degeneracy produces an energy cusp at $`\mathrm{\Delta }=0`$; $`n_D`$ changes discontinuously and the partial derivative in Eq. (2) is not defined. Finite rings with $`N`$ = 4n+2 have nondegenerate GS at $`\mathrm{\Delta }=0`$, no cusp and finite $`(n_D/\mathrm{\Delta })_0`$. The 4n, 4n+2 sequences must coincide in the extended chain and do so according to Eq. (4), with continuous $`n_D`$ and divergent $`(n_D/\mathrm{\Delta })_0`$. Exact $`U=0`$ results illustrate the extrapolation problems encountered in interacting chains.

The full basis of $`H_0(t,\mathrm{\Delta },U)`$ increases roughly as $`4^N`$ with $`N`$ and as $`3^N`$ when we exclude doubly ionized sites, i.e. two electrons at A sites or two holes at D sites. We use VB methods  to reach $`N`$ = 16 for the full basis and $`N`$ = 22 for the restricted basis. The basis has over $`10^7`$ singlets or $`10^9`$ Slater determinants with $`S_z=0`$. Exact solution  of the extended chain is limited to $`\mathrm{\Delta }=0`$, the Hubbard model. The GS is a nondegenerate singlet, the charge gap is finite for $`U>0`$ and there is spin-charge separation at large $`U`$. Finite $`t`$ and $`U`$ always lowers the energy in Fig. 1 compared to $`t=0`$. The greatest changes occur at $`\mathrm{\Delta }=\pm U/2`$, where $`t`$ cannot be treated as a small parameter.

In $`C_N`$ symmetry, the GS of the interacting systems transforms as $`k^{}=\pi `$ on the covalent side of 4n rings and as $`k^{}=0`$ in 4n+2 rings. Site energies $`\mathrm{\Delta }>0`$ lower the symmetry from $`C_N`$ to $`C_{N/2}`$ and yield a charge-density-wave (CDW) GS. The extended system no longer has inversion centers between sites, which corresponds to reflection between sites for finite $`N`$, but retains inversion at the sites or, for finite $`N`$, reflection $`\sigma _v`$ through the sites. With two sites per unit cell, both $`k^{}=0`$ and $`\pi `$ transform as $`k=0`$ in the first Brillouin zone. According to reflection through sites, the covalent GS of 4n+2 rings is even ($`\sigma _v=1`$, $`A_1`$) and that of 4n rings is odd ($`\sigma _v=1`$, $`A_2`$). The GS of 4n rings is degenerate at $`\mathrm{\Delta }_c(U,N)`$, where the symmetry switches from $`A_2`$ to $`A_1`$ with increasing $`\mathrm{\Delta }`$, and this crossover defines the NIT. In addition to PBC, we use antiperiodic boundary conditions (APBC) with reversed sign $`t_{1N}=1`$ for transfer between 1 and $`N`$. This corresponds to $`\varphi _{n+N}=\varphi _n`$ for the on-site wavefunctions and a periodicity 2$`N`$. In terms of VB diagrams, we modify $`\sigma _v`$ for reflection through sites 1 and $`N/2+1`$ to:

$$\sigma ^{}=\sigma _v(1)^{n_1}$$
(5)
where $`n_1`$ is the occupation number of site 1. The APBC GS has $`\sigma ^{}=1`$ in 4n rings for any $`\mathrm{\Delta },U`$. The GS of 4n+2 rings have a crossover from $`\sigma ^{}=1`$ at small $`\mathrm{\Delta }`$ to $`\sigma ^{}=1`$ at $`\mathrm{\Delta }>\mathrm{\Delta }_c(U,N)`$. The subspaces $`A_1^{},A_2^{}`$ associated with $`\sigma ^{}`$ do not coincide with $`A_1`$, $`A_2`$. The paired state is unique and even for either PBC or APBC. There are two covalent states, the Kekulé diagrams for benzene, with nearest-neighbor pairing of all spins. We define $`|K1`$ and $`|K2`$ as pairing spins at sites $`2i1`$, $`2i`$ and $`2i`$, $`2i+1`$, respectively, for all $`i`$. The pairing in $`|K1`$ is D+A-, while the pairing in $`|K2`$ is A- D+. The combination $`|K1+|K2`$ transforms as $`A_1`$ or $`A_2^{}`$ for PBC and APBC, respectively, while the out-of-phase combination transforms as $`A_2`$ or $`A_1^{}`$.

The $`U=\mathrm{\Delta }=0`$ crossover connects electrons paired as D+2A-2 or DA in Fig. 1. For $`U>0`$, the NIT shifts to positive $`U2\mathrm{\Delta }_c`$ and $`t0`$ preferentially stabilizes the paired GS over the covalent GS because the latter has finite probability for adjacent parallel spins that cannot transfer under Eq. (1). The symmetry changes at $`\pm \mathrm{\Delta }_c(U,N)`$ in rings with either PBC or APBC. Exact crossovers are shown in Fig. 2 as $`U2\mathrm{\Delta }_c(U,N)`$ in the $`U,\mathrm{\Delta }>0`$ quadrant for $`U`$ = 0.5, 1, 2, 3, 4, 5, and 10; the inset has $`U`$ = 100, 200, 300 and $`\mathrm{}`$, the last one corresponding to the restricted basis. At fixed $`U`$ and finite $`N`$, the crossovers are similar for 4n with PBC and 4n+2 with APBC. The dashed line is an extrapolation to the infinite chain discussed below. The covalent region is very narrow and the crossovers merge at $`U=0`$. The inset shows that $`\mathrm{\Delta }_c(U,N)`$ is nearly constant for $`\mathrm{\Delta }>5t`$.

We plot $`\mathrm{\Delta }_c(U,N)`$ vs. $`N^2`$ in Fig. 3 and find accurate extrapolation at large $`\mathrm{\Delta },U`$. The difference between $`U`$ = 300 and the restricted basis is due to small admixtures of A2-D2+ at energy $`U+2\mathrm{\Delta }`$. The extrapolated limit is $`U2\mathrm{\Delta }_c=`$ 1.332 in the restricted basis. It has previously been estimated  as 1.2-1.3 based on the singlet and triplet gaps, respectively, of $`N10`$ rings and  at 1.5 based on the ionicity up to $`N=10`$. Mixing with A2-D2+ grows as $`U`$ decreases, as seen for $`U=10`$, and the functional dependence is closer to $`N^1`$ at smaller $`U3`$. Kinetic contributions are largest at small $`U`$ and $`\mathrm{\Delta }`$, where $`t`$ is comparable to CT energies. The extrapolated (dashed) line in Fig. 2 is based on a power law, $`\mathrm{\Delta }_c(U,N)N^\gamma `$, with $`1<\gamma <2`$ giving the best fit for each $`U`$ from $`N`$ = 8 to 16.

Figures 2 and 3 indicate that, except for $`\mathrm{\Delta },U<2t`$, the NIT hardly varies with $`U/\mathrm{\Delta }`$. The relevant DA systems have narrow bands, oxides are modeled  with wider bands, $`\mathrm{\Delta }<t`$. The restricted basis captures the basic physics. We let both $`\mathrm{\Delta }`$ and $`U`$ diverge in $`H_0(t,\mathrm{\Delta },U)`$ while keeping $`\mathrm{\Gamma }=\mathrm{\Delta }U/2`$ finite  and reference the crossover to $`\mathrm{\Gamma }\mathrm{\Gamma }_c=\mathrm{\Delta }\mathrm{\Delta }_c`$. In the half-filled case, $`\mathrm{\Delta }\mathrm{}`$ ensures an electron at each D site and excludes two at any A site. The $`t=0`$ GS has energy $`2\mathrm{\Gamma }`$, 0 per DA on the paired and covalent side, respectively, with $`\mathrm{\Gamma }=0`$ at the NIT. The restricted basis is almost quantitative for $`U>5`$, makes larger $`N`$ accessible, and holds at the NIT. The related limit with both $`U`$ and $`U2\mathrm{\Delta }>>t`$ leads instead to a Heisenberg spin chain  without charge degrees of freedom and does not apply to the NIT.

The GS expectation value, $`n_{2i1}`$, for electrons at D sites is more accurate than the numerical derivative in Eq. (2). Matrix elements  over correlated states can be evaluated exactly for finite $`N`$. Results for the restricted basis of 4n rings with PBC and 4n+2 rings with APBC are shown as a function of $`\mathrm{\Gamma }\mathrm{\Gamma }_c(N)`$ in Fig. 4a. The crossover generates a jump in $`n_D`$. The charge density is continuous in $`A_1`$, $`A_2`$ for 4n rings, or in $`A_1^{}`$, $`A_2^{}`$ for 4n+2 rings, but continuing the lines in Fig. 4a through the NIT gives an excited-state density. All approaches to the NIT described by the hamiltonian in Eq. (1) indicate $`n_D`$ to be continuous when $`t`$ is finite. As expected, the discontinuity in $`n_D`$ decreases with $`N`$ and vanishes in the extended chain. The GS of 4n+2 rings with PBC or 4n rings with APBC remains in $`A_1`$ or $`A_1^{}`$, respectively, for any $`U,\mathrm{\Delta }`$ and the charge density is continuous, as shown in Fig. 4b. The NIT defined by the maximum of $`n_D/\mathrm{\Delta }`$ is less precise numerically (by $`0.02t`$) than a crossover. The curves in Fig. 4b have been adjusted to catch the extrapolation between increasing and decreasing series on either side of $`\mathrm{\Delta }_c`$. Results for the infinite chain are shown as stars that coincide in both panels. They represent joint extrapolations as either $`N^1`$ or $`N^2`$ that give the smaller mean square deviation. Indeed, $`n_D`$ is almost quantitatively known from the requirements that $`n_D(22)>n_D(20)`$ on the covalent side and $`n_D(22)<n_D(20)`$ on the paired side. The present estimate for $`n_D`$ is 1.314(2) at the NIT, i.e. $`\rho =0.684`$.

The restricted basis for $`U,\mathrm{\Delta }>>t`$ fixes $`n_D=1.31`$ at the NIT of Eq. (1). The slope $`n_D/\mathrm{\Delta }`$ is finite, but this is inconclusive by itself. Hückel rings show similar 4n, 4n+2 behavior and exact $`N`$ = 200 and 400 results are indistinguishable from $`n_D`$ in Eq. (4) at the resolution of Fig. (4). The origin must be magnified an order of magnitude to see the divergence of $`n_D/\mathrm{\Delta }=(^2E_0/\mathrm{\Delta }^2)/N`$ at $`\mathrm{\Delta }=0`$. This divergence signals the intrinsic instability of the $`U=\mathrm{\Delta }=0`$ chain to a site-CDW distortion that, however, is already broken at finite $`U=2\mathrm{\Delta }_c`$ in interacting systems. Extended chains with $`U>0`$ have finite $`n_D/\mathrm{\Delta }`$ at the NIT. By contrast, the Peierls instability to a bond-CDW is unconditional  for any $`t/U`$, because dimerization breaks reflection symmetry $`\sigma _v`$, as experimentally recognized in the initial TTF-CA studies .

The full basis of the Hamiltonian in Eq. (1) is required for small $`U`$ and exact results for $`n_D`$ or $`\mathrm{\Delta }_c(U)`$ are limited to $`N`$ = 16. We again have discontinuous $`n_D(\mathrm{\Delta },U)`$ in 4n rings with PBC and 4n+2 rings with APBC, and continuous $`n_D`$ for the opposite boundary conditions. We compare in Fig. 5 extrapolated $`n_D`$ for $`U=`$ 2, 5 and 10 with the exact $`U=0`$ result in Eq. (4). The arrows marking the NIT for finite $`U`$ are based on symmetry crossovers and extrapolations similar to Fig. 3. We have increasing $`n_D(\mathrm{\Delta }_c,U)`$ with $`U`$ and the limiting value of $``$1.3 is reached by $`U=5`$. Figure 5 shows the stabilization of covalent states with increasing $`U`$ and small NIT variations for $`\mathrm{\Delta },U>2`$.

## III  Energy gaps and localization at the NIT

The excitations of $`H_0(t,\mathrm{\Delta },U)`$ provide other evidences of the NIT. The paired and covalent states are diamagnetic and paramagnetic, respectively. A singlet-triplet gap, $`E_{ST}`$, opens  at the NIT between a band insulator with $`E_{ST}>0`$ and a Mott insulator with $`E_{ST}=0`$. The lowest singlet excitation, $`E_{SS}`$, is between the $`A_1`$ and $`A_2`$ GS; hence $`E_{SS}`$ vanishes  at the NIT. The transition is dipole allowed and is formally the CT excitation, but $`E_{SS}`$ rapidly loses oscillator strength on the covalent side. The charge degeneracy in Fig. 1 at $`U=2\mathrm{\Delta }`$, $`t=0`$ distinguishes between neutral and ionic complexes. The $`t>0`$ gaps near the NIT are not known and their simultaneous opening, as tacitly supposed for a single transition, is not assured nor agreed on . We report exact excitation thresholds near the NIT defined by GS crossovers. All symmetry considerations apply to the full basis for $`\mathrm{\Delta }>0`$.

Figure 6 reports $`E_{SS}(N)=E_2(N)E_1(N)`$, i.e. the energy difference between $`A_2`$ and $`A_1`$ GS, in the restricted basis as a function of $`\mathrm{\Gamma }\mathrm{\Gamma }_c(N)`$. Since $`E_{SS}(N)`$ increases in 4n rings for $`\mathrm{\Gamma }>\mathrm{\Gamma }_c`$ and decreases in 4n+2 rings, we have finite $`E_{SS}`$ on the paired side. On the covalent side, $`E_{SS}(N)`$ decreases with $`N`$ in rings whose GS remains in $`A_1`$ or $`A_1^{}`$ and increases in rings whose GS is in $`A_2`$ or $`A_2^{}`$. Joint extrapolations yield the stars that are consistent with vanishing $`E_{SS}`$ in the extended system. Exact results to $`N`$ = 22 in Fig. 6 are the most stringent limit to date, with $`E_{SS}<0.05t`$ on the covalent side and finite $`E_{SS}(N)`$ for $`\mathrm{\Gamma }\mathrm{\Gamma }_c<0.05t`$. We note that at $`\mathrm{\Delta }=0`$, far on the covalent side, Ovchinnikov  found nonpolar singlets with zero gap for any $`U>0`$. Far on the paired side, we have $`E_{SS}2\mathrm{\Gamma }`$ by inspection. Hence increasing $`\mathrm{\Delta }`$ at fixed $`U`$ in the extended system clearly opens an SS gap that is seen to coincide in Fig. 6 with the NIT defined by the symmetry crossover. The unconditional instability for dimerization on the covalent side is closely related to vanishing $`E_{SS}`$; the instability is conditional for a finite gap.

The magnetic gap $`E_{ST}`$ is to the lowest triplet for either PBC or APBC. As shown in Fig. 7, $`E_{ST}`$ increases rapidly with $`\mathrm{\Gamma }>\mathrm{\Gamma }_c`$ in the restricted basis and is small on the covalent side. Open circles represent boundary conditions with crossovers and systems whose $`E_{ST}`$ increases with $`N`$ at larger $`\mathrm{\Gamma }\mathrm{\Gamma }_c`$. Closed circles are for boundary conditions without crossovers and show decreasing $`E_{ST}`$ with $`N`$. The stars in Fig. 7 are joint extrapolations. The bound on $`E_{ST}`$ is $`E_{ST}<0.1t`$ for $`\mathrm{\Gamma }<\mathrm{\Gamma }_c`$ and the gap opens at $`\mathrm{\Gamma }_c`$ or slightly on the covalent side. At finite $`U`$, the extended system is rigorously known to be paramagnetic  at $`\mathrm{\Delta }=0`$, with $`E_{ST}=0`$, and diamagnetic with $`E_{ST}2\mathrm{\Delta }U`$ for $`\mathrm{\Delta }>>U`$. The opening of an ST gap with increasing $`\mathrm{\Delta }`$ is assured, and the results in Fig. 7 are consistent with $`E_{ST}>0`$ at the NIT. The concomitant dimerization on the covalent side opens a magnetic gap, as it is well known in spin chains  with regular or alternating exchanges and triplet spin excitons.

The charge gap of the Hamiltonian in Eq. (1) is $`IA`$, since there is not an explicit Madelung contribution. $`IA`$ is related to the GS of the cation and anion radicals, $`E_+(N)`$ and $`E_{}(N)`$, respectively, and corresponds to charge disproportionation or electron transfer between noninteracting systems,

$$I(N)A(N)=E_+(N)+E_{}(N)2E_0(N).$$
(6)
At $`t=0`$ and $`\mathrm{\Delta }>0`$, we have a paired GS for $`U<2\mathrm{\Delta }`$ with $`I=\mathrm{\Delta }U`$ and $`A=\mathrm{\Delta }`$; the lines cross at the NIT and the covalent side has $`I=\mathrm{\Delta }`$ and $`A=\mathrm{\Delta }U`$ for $`U>2\mathrm{\Delta }`$. For $`t>0`$, the charge gap of free electrons, $`|2\mathrm{\Delta }|`$, follows from the valence and conduction bands in Eq. (3); the extended $`U=0`$ system is metallic at $`\mathrm{\Delta }=0`$ and insulating otherwise. Although not known exactly for $`U>0`$, the charge gap is readily shown to be large, roughly $`|2\mathrm{\Delta }U|`$, far from the NIT. On the covalent side, it becomes the Lieb-Wu gap  at $`\mathrm{\Delta }=0`$ and increases as $`U`$ for $`U>4t`$; on the paired side, all gaps increase as $`2\mathrm{\Delta }U`$ for $`\mathrm{\Delta }>>U`$. Finite $`N`$ leads to charge gaps at the NIT in systems with discrete energies.

Both e-h symmetry  and $`\sigma _b`$ are broken for $`\mathrm{\Delta }>0`$, but their product remains a symmetry operation. Extended e-h symmetry  cuts basis, either full or restricted, roughly in half and corresponds in the $`S=0`$ manifold to the $`A_g^+B_u^{}`$ and $`A_g^{}B_u^+`$ subspaces of $`H_0(t,0,U)`$. The GS symmetry does not change at the NIT. E-h symmetry relates the GS and excited states of the radical ions . In particular, we have $`E_{}(N)=E_+(N)+U`$, a general result that holds on adding any spin-independent potential to $`H_0(t,\mathrm{\Delta },U)`$. It follows that Eq. (6) reduces to $`I(N)+A(N)=U`$ for even $`N`$ and arbitrary $`t,\mathrm{\Delta },U`$. Table 1 reports $`I(N)A(N)`$ at $`U,\mathrm{\Delta }_c`$ up to $`N`$ = 14 in the full basis and $`N`$ = 18 in the restricted basis. The $`U=0`$ gaps vanish at the crossover, where the electron transfer described in Eq. (6) involves degenerate orbitals. The charge gaps increase with $`U`$ but remain small at the crossover even for divergent $`U`$. The gaps in Table 1 follow power laws, $`N^\gamma `$, with $`\gamma <0.6`$ and place a rough bound of $`0.2t`$ on the extended system. The charge gap vanishes at most at a single point, $`\mathrm{\Delta }_c(U)`$ or $`U_c(\mathrm{\Delta })`$, that coincides with the NIT within the accuracy of finite systems.

The SS, ST and charge gaps are all finite on the paired side, $`\mathrm{\Gamma }>\mathrm{\Gamma }_c`$. They differ on the covalent side, however, where only the charge gap is finite. We associate gaps on the paired side with localization. The GS for the $`|\mathrm{\Delta }|>>U`$ limit has paired spins on either odd or even sites and is manifestly localized. Since gapless triplets and singlets are firmly established  at $`\mathrm{\Delta }=0`$, the GS of $`H_e(t,\mathrm{\Delta },U)`$ for $`U,t>0`$ is extended at $`\mathrm{\Delta }=0`$ and localized at $`\mathrm{\Delta }>>U`$. A localization-delocalization transition between two insulators incorporates all aspects of the NIT and the vanishing charge gap suggests a metal at the transition. We develop these ideas below.

To show localization on the covalent side, we partition $`H_0`$ in the restricted basis into $`h_0`$ for transfers between sites 2n-1 and 2n, as in $`|K1`$, and a perturbation $`V`$ for transfers between 2n and 2n+1. We take $`\mathrm{\Gamma }=\mathrm{\Delta }U/2>0`$ in units of $`t`$ and solve the 2x2 dimer problem in the singlet subspaces of $`h_0`$. The exact GS of $`h_0`$ is

$$|G_0(\mathrm{\Gamma })=\underset{i=1}{\overset{N/2}{}}\left[a_{2i1,\alpha }^+a_{2i1,\beta }^+\mathrm{cos}\varphi +\sqrt{2}\left(a_{2i1,\alpha }^+a_{2i,\beta }^+a_{2i1,\beta }^+a_{2i1,\alpha }^+\right)\mathrm{sin}\varphi \right]|0$$
(7)
where $`|0`$ is the vacuum state and $`\mathrm{tan}2\varphi =\sqrt{2}/\mathrm{\Gamma }`$ governs the mixing of $`|DA`$ and the singlet linear combination of $`|D^+A^{}`$. The zeroth-order energy is $`\mathrm{\Gamma }(\mathrm{\Gamma }^2+2)^{1/2}`$ per dimer. The opposite choice of 2n, 2n+1 for dimers has the same energy but admixes $`|A^{}D^+`$ singlets, as in $`|K2`$. Each dimer has a triplet with excitation energy $`ϵ_T=\mathrm{\Gamma }+(\mathrm{\Gamma }^2+2)^{1/2}`$, a singlet at $`ϵ_S=2(\mathrm{\Gamma }^2+2)^{1/2}`$ and strictly confined electrons. The perturbation

$$V=\underset{i,\sigma }{}\left(a_{2i,\sigma }^+a_{2i+1,\sigma }+a_{2i+1,\sigma }^+a_{2i,\sigma }\right),$$
(8)
is necessarily small when $`\mathrm{\Gamma }`$ is large. To second-order in $`V`$, the energy per dimer is

$$ϵ^{(0)}+ϵ^{(2)}=\mathrm{\Gamma }(\mathrm{\Gamma }^2+2)^{1/2}\frac{\mathrm{cos}^4\varphi +\frac{\mathrm{sin}^4\varphi }{4}}{(\mathrm{\Gamma }^2+2)^{1/2}}$$
(9)
Electrons are now confined to adjacent dimers that are connected by virtual excitations. As shown in Table 2, Eq. (9) is nearly quantitative as close to the NIT as $`\mathrm{\Gamma }=2`$. Localization to adjacent dimers approximates the exact solution of Eq. (1), which for $`N`$ = 22 is a linear combinations of over $`10^7`$ singlets. Rapid convergence with $`N`$ also points to localization on the paired side and is seen for $`n_D`$ in Fig. 4, $`E_{SS}`$ in Fig. 6 and $`E_{ST}`$ in Fig. 7. Successive orders in $`V`$ increase by one the number of coupled dimers. Such an expansion fails at the NIT or on the covalent side.

To see if the system is metallic at the transition, we compute the charge stiffness  relevant to the Hamiltonian in Eq. (1). This property has been applied to interacting fermions  in one dimension. The perturbation is a phase factor $`\mathrm{exp}(\pm if)`$ in Eq. (1) for transfers to the right and left ,

$$V(f)=(1\mathrm{cos}f)\nu _++i\nu _{}\mathrm{sin}f$$
(10)
The first term of Eq. (1) is $`\nu _+`$, while $`\nu _{}`$ has oppositely signed transfers to the right and left and connects $`A_1`$ and $`A_2`$ states for PBC. We now have $`E_0(\mathrm{\Gamma },t,f)`$ in units of $`t`$. The charge stiffness per site is $`\chi _{cs}=(^2E_0/f^2)_0/N`$. It is finite in conductors and vanishes in insulators. At the crossover, the proper zeroth-order GS of 4n rings is the odd linear combination of the $`A_1`$ and $`A_2`$ GS and

$$\chi _{cs}(\mathrm{\Gamma }_c)=\left(\frac{^2E_0}{Nf^2}\right)_0=p^{(1)}+p^{(2)}=\frac{|E_0|}{N}+\frac{\mathrm{\Gamma }_c(n_D^{(1)}+n_D^{(2)}2)}{2}$$
(11)
Here $`n_D^{(1)}`$ and $`n_D^{(2)}`$ are the electron densities at donor sites in the $`A_1`$ and $`A_2`$ subspaces, respectively, and $`p^{(1)}`$ and $`p^{(2)}`$ are the corresponding bond orders, with $`2p`$ defined as the GS expectation value of $`\nu _+`$, which we evaluate in the restricted basis. The donor densities at the NIT are shown in Fig. 4 and have opposite $`N`$ dependence in $`A_1`$ and $`A_2`$. The value of $`\mathrm{\Gamma }_c=U/2\mathrm{\Delta }_c=0.666`$ follows from Fig. 3. We have a poor metal: $`\chi _{cs}(\mathrm{\Gamma }_c)0.74`$ is $``$60% of $`4/\pi `$ value for free electrons at $`\mathrm{\Delta }=U=0`$ in Eq. (1). For $`\mathrm{\Gamma }\mathrm{\Gamma }_c`$, second-order perturbation theory in $`f`$ becomes exact . Fig. 8 shows that $`\chi _{cs}(\mathrm{\Gamma })`$ is exponentially small on either side of the NIT. The charge stiffness  of the Hubbard model has a similar peak at $`U=0`$ that narrows with $`N`$ and becomes a $`\delta `$-function in the infinite chain. Hence we expect $`\chi _{cs}(\mathrm{\Gamma })`$ to vanish except at $`\mathrm{\Gamma }_c`$ in the extended system.

A metallic point connecting insulating phases has been recently discussed for $`H_0(t,\mathrm{\Delta },U)`$  and for the following half-filled system of spinless fermions ,

$$H=\underset{i}{}(a_i^+a_{i+1}+a_{i+1}^+a_i)+\underset{i}{}(𝒱n_in_{i+1}+𝒲n_in_{i+2})$$
(12)
Large $`𝒱>0`$ favors a GS without adjacent occupied sites, while large $`𝒲`$ favors one with adjacent filled and empty sites along the chain. The $`t=0`$ crossover occurs at $`𝒱=2𝒲`$, with adjacent electrons and holes for $`𝒱<2𝒲`$ that resemble D and A sites, respectively. The $`𝒱>2𝒲`$ GS has alternating filled and empty sites that, taken in pairs, correspond to D+ and A-. The crossover is not precisely at $`𝒱=2𝒲`$, presumably due to different bond orders in the two GS. It shifts to $`𝒲𝒱/20.6`$ in units of $`t`$, very close to $`\mathrm{\Gamma }_c`$. Transfers between two sites in Eq. (12) differ from spin degeneracy in Eq. (1), however, and the models do not map into each other. Exact results  to $`N`$ = 40 for Eq. (12) are comparable to $`N`$ = 20 for the full basis of Eq. (1). The striking similarity between Fig. 8 and the charge stiffness of Eq. (12) up to $`N`$ = 40 suggests a similar interpretation.

## IV discussion

The modified Hubbard model in Eq. (1) has many applications to both theory and experiment. With variations, it is suitable for modeling valence transitions, excitation thresholds, electronic or structural instabilities, among other topics. Its two parameters, $`U/t`$ and $`\mathrm{\Delta }/t`$, encompass the Hubbard model ($`\mathrm{\Delta }=0`$) at half or other filling, two bands at $`U=0`$ and localized dimers for $`\mathrm{\Delta }>>U`$. At fixed $`U`$ and $`t`$, increasing $`\mathrm{\Delta }>0`$ generates a neutral-ionic transition whose characterization is the principal goal of this paper. The NIT of the Hamiltonian in Eq. (1) has continuous ionicity given by Eq. (2) and excitation gaps for singlets, triplets and charges that are not known exactly. Previous approximations have been developed separately for $`n_D`$, $`E_{SS}`$, $`E_{ST}`$, the charge gap, the GS at the NIT, instabilities, etc. Our collective analysis of symmetry crossovers, excitation thresholds and GS properties incorporates computational advances and yields better estimates for extended systems.

Finite-size results require extrapolations whose accuracy improves with $`N`$. We followed the NIT of $`H_0(t,\mathrm{\Delta },U)`$ through the symmetry crossover of the GS, the charge density $`n_D`$, the excitations $`E_{SS}`$, $`E_{ST}`$, and the charge gap and stiffness. Larger $`N`$ is accessible in the restricted basis allowing for an accurate estimate of $`\mathrm{\Gamma }_c=0.666t`$ from the crossover and setting stringent limits of $`0.1t`$ for the opening of all three gaps at this position. Thus the numerical results point to a single transition. The NIT of the modified Hubbard model is continuous, as previously found, and is marked by the opening of singlet, triplet and charge gap on the paired side. There is no gap in the singlet or triplet manifold on the covalent side. The interacting system is known to have a delocalized GS at $`\mathrm{\Delta }=0`$, the Hubbard limit, and localized GS for $`\mathrm{\Delta }>>U`$, the paired limit. We identify the NIT at $`\pm \mathrm{\Delta }_c(U,t)`$ as the appearance of a localized GS.

Resta and Sorella discuss  polarization and metallic behavior at the NIT in the context of oxides, with $`t_0`$ = 3.5 eV, $`\mathrm{\Delta }^{}`$ = 2.0 eV and variable $`U`$ in Eq. (1). The crossover in $`N`$ = 8 rings, at $`U/t_0=2.27`$, is used to estimate the polarization of extended systems. Since $`\mathrm{\Delta }^{}/t_0`$ = 0.571 corresponds to large $`t`$, the crossover is near the origin of the $`\mathrm{\Delta },U`$ plane in Fig. 2 and there are substantial finite-size effects. The $`N`$ = 8 result in Fig. 2 yields $`U_c=2.27`$, in quantitative agreement with ref. , but larger $`N`$ up to 16 extrapolate to larger $`U_c/t`$ = 2.70 for the extended system. Such corrections are consistent with $`N10`$ results on CT complexes. The GS polarizability is a new approach, different from the charge stiffness, to the identification of metallic behavior.

The GS density is $`n_D`$ = 1.314 at the NIT of the restricted basis, when one electron is always confined to D. The spin degeneracy of D+ or A- spoils exact analysis. The degeneracy of charge and spin excitations at the NIT gives a simple, heuristic interpretation: $`n_D=4/3`$ is the result for equal weights of molecules and spin-1/2 radical ions. Equal weights at the NIT can be justified rigorously at $`U=0`$ for electrons or for spinless fermions, but not in the restricted basis. We found $`\mathrm{\Gamma }_c`$ = -0.666 in the restricted basis and use this value in $`|G_0(\mathrm{\Gamma })`$, the dimer GS in Eq. (7); the paired-state amplitude is $`\mathrm{cos}^2\varphi `$= 0.287, which corresponds to $`n_D`$ = 1.287. Dimers capture most of the configuration mixing of the extended system. The full basis has contributions from D2+ and A2- diagrams, which as seen in Fig. 5 reduce $`n_D`$ compared to the restricted basis.

Peierls-Hubbard models are widely applied to structural instabilities. The stability of the GS to a perturbation can be formulated in terms of susceptibilities, $`\chi `$, that are formally given by the exact eigenstates $`|F`$ and energies $`E_F`$ of the hamiltonian in Eq. (1). The perturbation is written as the product $`\theta Q`$, where $`\theta `$ is the relevant operator for coupling to $`Q`$, and the corresponding $`\chi `$ is

$$\chi \left(\frac{^2E_G}{Q^2}\right)_0=2\underset{F}{}\frac{|G|\theta |F|^2}{E_FE_G}$$
(13)
Since the sum is over the excited states of the unperturbed system, the eigenstates of the uniform chain in Eq. (1) suffice for the stability of the modified Hubbard model. The charge stiffness in Eq. (12) is $`\chi `$ with respect to a magnetic field perpendicular to the ring  and gives information about current flow. Structural transitions are investigated by introducing phonons as $`Q`$-perturbation. The Peierls instability for dimerization involves $`k=0`$ phonons with $`\theta `$ representing the staggered bond-order operator (the first term in Eq. (1), augmented by a $`(1)^i`$ factor). This operator breaks inversion symmetry at the sites and mixes $`A_1`$ and $`A_2`$ singlets . Vanishing $`E_{SS}`$ on the covalent side of the NIT then indicates a divergent $`\chi `$ and the unconditional instability of a lattice with harmonic potentials . On-site (Holstein) phonons couple instead to CDW operator $`n_D`$. Since $`\chi _\mathrm{\Delta }=n_D/\mathrm{\Delta }`$ is finite at the NIT, except for $`\mathrm{\Delta }=0`$, the corresponding instability is conditional ; the NIT marks the maximum $`\chi _\mathrm{\Delta }`$, i.e. the maximum $`n_D/\mathrm{\Delta }`$, as discussed under Fig. 4.

We turn next to open or controversial aspects of the NIT of the modified Hubbard model. Some authors  have proposed two transitions related to the closing of charge and spin gaps, respectively; a spontaneously dimerized phase then separates a band insulator corresponding to the paired GS and Mott insulator on the covalent side . The suggestions  for another transition rest on the analogy with spin-1/2 Heisenberg antiferromagnetic chains with frustration due to a second-neighbor exchange $`J_2`$. The Kekule diagram $`|K1`$ or $`|K2`$ is the exact GS at $`J_2=J_1/2`$, as recognized by Majumdar . There is no exact mapping of Eq. (1) into such a spin chain, not even at large $`U`$, but the GS of related models with, for example, second-neighbor transfers have not been studied in detail. Our exact results for $`H_0(t,\mathrm{\Delta },U)`$ with finite $`N`$ show that the maximum of $`\rho /\mathrm{\Delta }`$, the closing of the singlet and triplet gaps, and the vanishing of the charge gap coincide at the NIT within $`0.1t`$. Finite systems cannot specify transitions, but provide some constraints. The Mott insulator dimerizes spontaneously for any $`t/U`$, as discussed for the spin-Peierls instability  of Heisenberg antiferromagnetic chains. The dimerization amplitude becomes very small for $`U>>t`$ and $`J=t^2/U`$, since the electronic stabilization is less than $`J`$, but the singularity actually increases ; the GS energy in Eq. (3) at $`U=\mathrm{\Delta }=0`$ goes as $`\delta ^2\mathrm{ln}\delta `$ for alternating $`t(1\pm \delta )`$ along the chain, while the GS of the spin chain with alternating $`J(1\pm \delta )`$ goes as $`\delta ^{4/3}\mathrm{ln}\delta `$ . Such considerations apply to Eq. (1) in the covalent limit $`\mathrm{\Gamma }=U2\mathrm{\Delta }>>t`$ where, as noted originally , we have a Heisenberg chain with $`J=t^2/\mathrm{\Gamma }`$.

The charge gap is a recent topic and is expected to have a minimum at NIT . We find finite minima in interacting systems with finite $`N`$. As already noted, the polarizability  and the charge stiffness in Eq. (12) and Fig. 8 give independent indications of a metallic GS at the NIT. We consequently expect vanishing charge gap there. The metal separating two insulating phases is extremely fragile: not only is it restricted to a single point $`\mathrm{\Delta }_c(U)`$, but it is unconditionally unstable to dimerization. Moreover, extending the model in Eq. (1) to include intersite e-e interactions or on-site phonons produces a discontinuous NIT above some critical coupling, which excludes a metallic phase even for a rigid lattice. By contrast, a metallic GS at the NIT of Eq. (1) is fairly robust. We have a simple half-filled band at $`U=0`$ and a correlated metal persists to arbitrarily large $`U`$. At the NIT, $`\mathrm{\Delta }`$ counterbalances $`U`$: the charge distributions DA and D+A- are almost degenerate and hence strongly mixed by any finite $`t`$. A metallic state at NIT is not consistent with finite triplet excitation there.

The degeneracy of charge and spin excitations is characteristic of the NIT and appears already in the $`t=0`$ limit of Fig. 1. Finite $`\mathrm{\Delta }`$ completely spoils spin-charge separation at the NIT of Eq. (1). Vanishing $`E_{ST}`$ is closely linked to magnetic susceptibility of Hubbard or Heisenberg chains. Since a singlet can always be constructed from two triplets, vanishing $`E_{SS}`$ follows immediately and is associated with even-parity spin waves in $`\mathrm{\Delta }=0`$ systems with e-h symmetry. This symmetry is broken in Eq. (1) or its extensions, and the CT excitation connecting the $`A_1`$ and $`A_2`$ GS is dipole allowed. Spin-charge separation is regained on the covalent side when the charge gap exceeds a few $`t`$, much as in Hubbard models for $`U>t`$: Exact separation requires infinite $`U`$, but $`U>4t`$ suffices in practice.

To summarize, we have extended exact solutions of the modified Hubbard model in Eq. (1) to larger systems, identified the NIT with symmetry crossovers in rings with periodic or antiperiodic boundary conditions, and found the charge density, excitation thresholds and susceptibilities at the NIT. We find a continuous NIT and tighten considerably the extrapolated limits for the infinite chain. Our results indicate a T=0K transition with vanishing singlet and triplet gaps on the covalent side, vanishing charge gap and metallic GS at the NIT, and finite singlet, triplet and charge gaps on the paired side, whose localized GS is confirmed. We associate the NIT of the model in Eq. (1) with a transition from a delocalized (small $`\mathrm{\Delta }`$) to a localized (large $`\mathrm{\Delta }`$) GS. Accurate analysis of the hamiltonian in Eq. (1) is required to model valence transition in charge-transfer salts or metal oxides where long-range Coulomb interactions and e-ph coupling have to be considered explicitly.

ACKNOWLEDGMENTS

One of us (A.P.) thanks A.Girlando for helpful discussions, and J.Voit for exchanging interesting correspondence on the subject and for sharing information on unpublished work. We gratefully acknowledge support for work at Princeton from the National Science Foundation through DMR-9530116 and the MRSEC program under DMR-9400362, and, for work in Parma from the Italian National Research Council (CNR) within its “Progetto Finalizzato Materiali Speciali per Tecnologie Avanzate II”, and by the Ministry of University and of Scientific and Technological Research (MURST).