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# A quantitative theory-versus-experiment comparison for the intense laser dissociation of H⁺₂.

## I Introduction

The above threshold multiphoton ionization and dissociation of H$`{}_{}{}^{+}{}_{2}{}^{}`$ subjected to strong laser interaction, have revealed interesting nonlinear effects in angularly resolved kinetic energy distributions of the photofragments, measured in experimental works covering the last decade 1 ; 2 ; 3 ; 4 ; 5 . Among these are the observations of very large increase (or sometimes decrease) of the photodissociation rates originating from some vibrational states of the parent molecule at some specific laser intensities or, even more unexpectedly, misalignment effects in fragments angular distributions 6 . The interpretation of such behaviors has been attempted by referring to some basic dynamical mechanisms evidenced through the light-induced adiabatic potentials describing the dressed states of the molecule-plus-field system. According to the frequency regimes, bond softening (in UV) 1 ; 7  or barrier suppression (in IR) 8  mechanisms tend to enhance the dissociation cross-section especially in the polarization direction of the laser. As opposite to them vibrational trapping (in UV) 9  or dynamical dissociation quenching (in IR) 10 , act as stabilization mechanisms, favoring misalignment in the fragments distributions. This complementarity has also been referred to, for laser control purposes of the chemical reactivity; namely by softening some bonds while hardening others 11 . Although very accurate quantum calculations in the frame of time dependent approaches have been carried out, with successful interpretations of dynamical behaviors in short-intense laser pulses, to the best of our knowledge, there is no a thorough and quantitative theory-versus-experiment comparison, up to date, the work of Kondorskiy et al. Kondorskiy  being a precursor in this direction. Basically two reasons can be invoked for the difficulty of such an attempt: only very few theoretical models take into account the competition between ionization and dissociation processes leading, in very strong fields, to Coulomb explosions and only very few experimental works are conducted with a careful investigation of vibrational populations and sufficiently high momentum and angular resolution yielding accurate information about the dissociation of single vibrational levels.

Experimental works on this system can be classified according to the preparation of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$ from the neutral molecule H2. A first category collects experiments referring to optical ionization with a laser prepulse 1 ; 2 ; 3 ; 4 . The independence of the ionization and dissociation processes can not be experimentally controlled, and their competition is still an open question 5 . More recently, another kind of approach has been investigated through ion beam experiments, where H$`{}_{}{}^{+}{}_{2}{}^{}`$ ions are produced in a dc electric or plasma discharge that disentangle ionization and dissociation processes 12 ; 13 . An accelerated and strongly collimated monochromatic H$`{}_{}{}^{+}{}_{2}{}^{}`$ beam is crossed at right angle by a focused intense laser beam. An advantage of the strong ion beam collimation is the reduction of the intensity volume effect; all ions being approximately irradiated by the same laser intensity (the validity of such approximation will however be discussed hereafter). Moreover, experiments conducted with low intensity pulses coupled to computational simulations of the resulting dissociation spectra, allow the determination of the population of the rovibrational levels of H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecules in the beam. The neutral dissociation fragments (H atoms originating from photodissociation of H$`{}_{}{}^{+}{}_{2}{}^{}`$) are projected on a multichannel detector (MCD), whereas the charged particles (undissociated H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecules and H+ fragments) are extracted by deflection into a Faraday cup using an electric field. Excellent energy resolution (about 1%) allows the separation, in the circularly shaped patterns observed on the screen, the momentum projection of fragments almost originating from a single vibrational level 12 .

A model aiming in a quantitative theory-versus-experiment comparison, within the frame of the ion beam setup, has to fulfill the following requirements:

i) the photodissociation process has to be accurately described in the center of mass frame by a wavepacket propagation under the effect of an intense radiative field, starting from a given rovibrational state. There is no need, however, to refer to any competition with ionization, as the experiment precisely disentangles these two fragmentation processes.

ii) a geometrical transformation towards the MCD-plate has to be carried out, taking into account the macroscopic kinetics of the ion beam. This relates the total number of particles collected by a given pixel of the plate, during the whole experiment, to the previously calculated wavepacket, describing the evolution of an initial rovibrational state under the effect of a laser pulse of a given intensity.

iii) although particular attention has been paid to the ion beam collimation in order to reduce the field intensity volume effects, a spatial average over the laser focusing area has to be carried, taking into account the different radiative couplings felt by H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecules according to their geometrical position in the beam. This can be done through the use of some experimental measurements of the intensity distribution in the focus carried through a pinhole of 1 $`\mu `$m diameter 12 .

iv) quantitative agreement also requires an averaging on the detector plate using some windowing functions that simulate the resolution power of the detector.

The organization of the paper follows these achievements in Section II. The results and their interpretation are presented in Section III with a thorough discussion of the role of the intensity volume effect. An excellent theory-versus-experiment agreement is obtained not only for the kinetic but also on the angular distributions of the photofragments. Section IV is devoted to some conclusions and perspectives.

## II Theory

Referring only to two radiatively coupled Born-Oppenheimer electronic states; namely the ground (1s$`\sigma _g`$) and the first excited (2p$`\sigma _u`$), an accurate wavepacket propagation method using the split operator technique is described in detail in ref.14 ; 15 . For the sake of completeness, we give hereafter a brief summary of the method, introducing the corresponding coordinates, operators and quantum numbers. The emphasis is rather put on the way to relate the quantum information content of the wavepacket to the observed momentum projections of the neutral photofragments H resulting from a rovibrational distribution of parent ions H$`{}_{}{}^{+}{}_{2}{}^{}`$ excited by a laser source of given spatial distribution.

### II.1 The wavepacket propagation

In the laboratory frame and using spherical coordinates, the total molecule-plus-field Hamiltonian is written in terms of a two-by-two operator matrix:

$$𝐇(R,\theta ,\varphi ;t)=𝐓_R+𝐓_\theta +𝐓_\varphi +𝐕(t).$$
(1)
$`𝑹`$ is the diatomic internuclear vector. $`R`$, $`\theta `$ and $`\varphi `$ designate the internuclear distance, polar and azimuthal angles of $`𝑹`$ with respect to the laser polarization vector $`\mathit{ϵ}`$, respectively. As is usually done, a functional change on the wavepacket:

$$𝚿(R,\theta ,\varphi ;t)=\frac{1}{R}𝚽(R,\theta ,\varphi ;t)$$
(2)
aiming in a simplification of the radial part of the kinetic operators, leads to:

$$𝐓_R=\mathrm{𝟏}\frac{1}{2}\frac{^2}{R^2};$$
(3a)
$$𝐓_\theta =\mathrm{𝟏}\frac{1}{2R^2}\frac{1}{\mathrm{sin}\theta }\frac{}{\theta }\left(\mathrm{sin}\theta \frac{}{\theta }\right);$$
(3b)
$$𝐓_\varphi =\mathrm{𝟏}\frac{1}{2R^2}\frac{1}{\mathrm{sin}^2\theta }\frac{^2}{\varphi ^2}$$
(3c)
with $`\mathrm{𝟏}`$ the identity (2$`\times `$2) operator matrix. Atomic units ($`\mathrm{}`$=1) are used in Eqs(3) where $``$ designates the reduced mass. The time dependence arises in the non-diagonal terms of the potential energy operator matrix $`𝐕`$ through the radiative couplings:

$$V_{12}(R,\theta ,t)=\mu (R)(t)\mathrm{cos}\theta ,$$
(4)
where $`\mu (R)`$ is the transition dipole moment and $`(t)`$ is the laser electric field amplitude, given as product of a pulse shape $`ϵ(t)`$ times an oscillatory term involving the carrier wave frequency $`\omega `$:

$$(t)=ϵ(t)\mathrm{cos}\omega t.$$
(5)
Note that the $`\mathrm{cos}\theta `$ in Eq.(4) results from the dot product of the transition dipole vector (parallel to $`𝑹`$) times the laser polarization vector $`\mathit{ϵ}`$.

The diagonal elements $`V_1(R)`$ and $`V_2(R)`$ of $`𝑽`$ are nothing but the BO curves of the ground (label 1) and first excited (label 2) states of H$`{}_{}{}^{+}{}_{2}{}^{}`$. $`V_1`$, $`V_2`$ and $`\mu `$ are obtained in the frame of the Born-Oppenheimer approximation, at the zero order level with respect to the ratio $`m_e/m`$ of the electron to the proton masses. Using spheroidal coordinates, it is well known that the Schrödinger equation can be written as two eigenvalue equations 16a ; 16b , which have been numerically solved here using the shooting method 16c . The potential energy curves have been computed in the range 0 $`<R<`$ 200 a.u., with a numerical accuracy checked to be better than 10-12 a.u. The mass ratio $`m/m_e`$ has been taken as $`m/m_e`$ = 1836.152701. Finally the dipole matrix element $`\mu `$ between the $`1s\sigma _g`$ and $`2p\sigma _u`$ states has been obtained by numerical integration of the wave functions, at the same level of numerical accuracy.

The time dependent Schrödinger equation (TDSE) describing the wavepacket propagation is:

$$i\frac{}{t}𝚽(R,\theta ,\varphi ;t)=𝐇(R,\theta ,\varphi ;t)𝚽(R,\theta ,\varphi ;t)$$
(6)
with, as an initial condition:

$$𝚽(R,\theta ,\varphi ;t=0)=\left(\begin{array}{c}\mathrm{\Phi }_1(R,\theta ,\varphi ;0)\\ 0\end{array}\right)$$
(7)
reflecting the fact that at time $`t=0`$, only the ro-vibrational levels of the ground electronic state are populated. The eigenfunction $`\mathrm{\Phi }_1`$ precisely corresponds to such a state with quantum numbers $`g`$, $`v`$, $`N`$, $`M_N`$ (electronic ground, vibrational, total and $`\mathit{ϵ}`$-projected rotational) and is given by:

$$\mathrm{\Phi }_1(R,\theta ,\varphi ;0)=\chi _{g,v,N}(R)P_N^{M_N}(\mathrm{cos}\theta )e^{iM_N\varphi }.$$
(8)
$`P_N^{M_N}(\mathrm{cos}\theta )`$ is the ($`N`$,$`M_N`$) Legendre polynomial, whereas the radial part is defined as the solution of the time-independent Schrödinger equation:

$$\left[\frac{1}{2}\frac{\mathrm{d}^2}{\mathrm{d}R^2}+V_1(R)+\frac{N(N+1)}{2R^2}E_{v,N}\right]\chi _{g,v,N}(E)=0.$$
(9)
The motion associated with the azimuthal angle $`\varphi `$ remains separated under the action of the $`\varphi `$-independent $`𝑽`$, such that $`M_N`$ is a good quantum number describing the invariance through rotation about $`\mathit{ϵ}`$.

The propagation using the split-operator technique has been described in full detail in previous works 14 ; 15 ; 17 . The peculiarity of odd-charged homonuclear ions is their linearly increasing dipole moment with R, leading to asymptotically divergent radiative couplings. We take them into account by splitting the wavefunction into two regions, an internal and an asymptotic one. The latter is analyzed by a generalization of the Volkov type solutions 18 , while the numerical propagation on the former is performed by Fourier transform methodology 19  with the implementation of a unitary Cayley scheme for $`T_\theta `$ 17 .

### II.2 From wavepacket to observed spectra

The main concern of this paragraph is to relate the experimental observable, i.e. the probability distribution of hydrogen atoms resulting from H$`{}_{}{}^{+}{}_{2}{}^{}`$ photodissociation, as recorded on the multichannel detector (MCD), to the asymptotic part of the wavepacket $`𝚽(R,\theta ,\varphi ;t)`$ solution of Eq.(6). By asymptotic we mean large internuclear distances $`R`$ for which the molecule is considered as dissociated without the possibility of a recombination process. To the best of our knowledge such a correlation has not rigorously been attempted in the literature. So far, the interpretation of general tendencies of photodissociation spectra referring to basic mechanisms, has rather been conducted by angularly resolved kinetic energy distribution given by:

$$𝒫(k,\theta ,\varphi )=\underset{t\mathrm{}}{lim}\left|\widehat{\mathrm{\Phi }}(k,\theta ,\varphi ;t)\right|^2,$$
(10)
where

$$\widehat{\mathrm{\Phi }}(k,\theta ,\varphi ;t)=\frac{1}{\sqrt{2\pi }}_{\mathrm{}}^{\mathrm{}}\mathrm{\Phi }(R,\theta ,\varphi ;t)e^{ikR}dR.$$
(11)
is the Fourier transform of $`\mathrm{\Phi }`$ over the scalar variable $`R`$, (i.e. not over $`𝑹`$ taken as a vector). The argument retained by doing so, is that asymptotically, due to $`R^1`$ type of behavior in the kinetic operators Eqs(3b,3c), angular dynamics is not affected at large internuclear distances. Note that in this paragraph, for the sake of simplicity, we drop the labels of $`𝚽`$ depicting initial state quantum numbers ($`v`$, $`N`$, $`M_N`$).

To reach a comparative level of understanding, we are now describing the two families of experiments. Pertaining to the first family are photodissociation experiments where both photodissociation and photoionization steps are laser induced 1 ; 2 ; 3 ; 4 . Starting from neutral H2, in its ground electronic and vibrationless state X($`v`$=0), a multiphoton excitation leads, through the EF intermediate excited electronic state, to the H$`{}_{}{}^{+}{}_{2}{}^{}`$ ground state with a distribution of rovibrational levels. Dissociation follows the absorption of additional photons and is very fast as compared to the relative motion of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$ in the laboratory frame. Whence the photofragments are well separated, H+ ions are extracted (accelerated) through an electric field and collected on the MCD plate. A schematic view is provided in figure 1. Photodissociation occurs, as a fast process, at the origin $`O`$ of the laboratory frame, at a time which is taken as $`t=0`$. The laser polarization vector is along the $`z`$-direction, $`𝒓_\mathrm{𝟏}`$ and $`𝒓_\mathrm{𝟐}`$ are the vectors pointing H and H+. A further step is the extraction of the proton H+ by an electric field applied along the $`𝒚`$-direction towards the MCD plate positioned at a distance $`OO^{}`$=$`D`$ from the origin. The detection occurs on a pixel $`M`$ defined by its polar coordinates ($`\rho `$, $`\alpha `$) on the MCD surface (or by $`𝒓`$ with respect to $`O`$) that H+ is reaching after a time of flight $`t`$, with velocity $`v`$. It is worthwhile noting that this last step is just a mapping of the photofragment onto the detector (without dissociation during time $`t`$). The vector transformation relating the proton H+ position ($`R,\theta ,\varphi `$) in the center of mass frame to the pixel M ($`\rho ,\alpha `$) on the detector is known as the Abel transformation 23 .

A different situation prevails in the experiments of the second family where an electric or a plasma discharge ionizes H2 into H$`{}_{}{}^{+}{}_{2}{}^{}`$ 12 ; 13 . The resulting ion beam is strongly accelerated by an electric field and is crossed at $`t=0`$ by the laser beam at a point $`O`$ of the laboratory frame. The description of such experiments, as illustrated in figure 2, has to combine two motions; namely, the translation of the center of mass $`G`$ in the laboratory frame along $`𝒖_𝒚`$ (unit vector along $`𝒚`$) with velocity $`v`$ and the nuclear separation (dissociation) in the center of mass frame. The hydrogen atom H resulting from photofragmentation is collected at the pixel $`M`$ of the detector. It is to be noted that $`M`$ is positioned with respect to the laboratory frame with a vector $`𝒓`$, corresponding to $`𝒓_\mathrm{𝟏}`$ at time $`t`$, when H reaches $`M`$.

As, our concern is the quantitative interpretation of photodissociation spectra obtained in H.Figger’s group using an electric discharge to induce ionization 12 ; 20 ; 21 , emphasis is put in the following on a thorough description of the kinematics of the second family experiments. The quantity which is measured, is nothing but the number of hydrogen atoms $`\mathrm{d}N`$ collected on each pixel $`M`$ ($`\rho `$, $`\alpha `$) at infinite time. This can ultimately been related with the time integral of the flux of the current density $`𝒋(\rho ,\alpha ,t)`$ of H orthogonal to the area $`\mathrm{d}S=\rho \mathrm{d}\rho \mathrm{d}\alpha `$ of the finite size pixel $`M`$, as

$$\mathrm{d}N(\rho ,\alpha )=N\mathrm{d}S_0^{\mathrm{}}𝒋(\rho ,\alpha ,t)𝒖_𝒚dt,$$
(12)
where $`N`$ is the total number of H photofragments. The flux in Eq.(12), involves an averaging over the positions of all protons H+ that are not detected in the experiment 125 :

$$𝒋(t)=\frac{1}{m}d𝒓_\mathrm{𝟐}\mathrm{Im}\left[\mathrm{\Psi }^{}(𝑹,𝑹_𝑮;t)_{𝒓_\mathrm{𝟏}}\mathrm{\Psi }(𝑹,𝑹_𝑮;t)\right].$$
(13)
where $`\mathrm{\Psi }(𝑹,𝑹_𝑮;t)`$ is the overwhole wavepacket describing the combined molecular internal $`𝑹`$-motion and center of mass $`𝑹_𝑮`$-motion. $`\mathrm{Im}`$ stands for the imaginary part. Frame transformations defining $`𝑹_𝑮`$ and some vector relations directly related with figure 2, are gathered in an Appendix. Separation of the photofragments relative motion described by $`\mathrm{\Psi }(𝑹;t)`$, from the motion of the center of mass described by $`\mathrm{\Phi }_G(𝑹_𝑮;t)`$, leads to the following representation of the total wavefunction:

$$\mathrm{\Psi }(𝑹,𝑹_𝑮;t)=\mathrm{\Psi }(𝑹;t)\mathrm{\Phi }_G(𝑹_𝑮;t).$$
(14)
Using the frame transformations Eqs(A-1,A-2) together with Eq.(2) one has:

$$\mathrm{\Psi }(𝑹,𝑹_𝑮;t)=\frac{\mathrm{\Phi }(𝒓_\mathrm{𝟏}𝒓_\mathrm{𝟐};t)}{𝒓_\mathrm{𝟏}𝒓_\mathrm{𝟐}}\mathrm{\Phi }_G(\frac{(𝒓_\mathrm{𝟏}+𝒓_\mathrm{𝟐})}{2};t).$$
(15)
Concerning the calculation of the gradient $`_{𝒓_\mathrm{𝟏}}`$ involved in Eq.(13), we note that the flux has to be evaluated at large $`R`$ with as consequences:

$$_{𝒓_\mathrm{𝟏}}\mathrm{\Phi }(𝑹;t)=_𝑹\mathrm{\Phi }(𝑹;t)𝒖_𝑹\frac{}{R}\mathrm{\Phi }(𝑹;t)$$
(16)
with $`𝒖_𝑹`$ the unit vector along $`𝑹`$ (Eq.(A-6)) and

$$_{𝒓_\mathrm{𝟏}}\mathrm{\Phi }_G(𝑹_𝑮;t)=\frac{1}{2}_{𝑹_𝑮}\mathrm{\Phi }_G(𝑹_𝑮;t)$$
(17)
The approximation involved in Eq.(16) results from the neglect of all angular derivations due to their occurrence with coefficients decreasing faster than $`R^1`$. We proceed now to a quasiclassical approximation for the description of the center of mass translational motion, with two implications:

(i) $`𝑹_𝑮v𝒖_𝒚t`$ has a corresponding wavevector $`𝑲_𝑮mv𝒖_𝒚`$ and the application of momentum operator $`i_{𝑹_𝑮}`$ to $`\mathrm{\Phi }_G(𝑹_𝑮)`$ simply result into $`mv\mathrm{\Phi }_G(𝑹_𝑮)`$. When this is done at the level of Eq(13) one gets:

$$𝒋(t)=\frac{1}{m}𝑑𝒓_\mathrm{𝟐}\frac{1}{|𝒓_\mathrm{𝟏}𝒓_\mathrm{𝟐}|^2}\mathrm{Im}\left[\mathrm{\Phi }^{}(𝑹;t)\frac{}{R}\mathrm{\Phi }(𝑹;t)+imv|\mathrm{\Phi }(𝑹;t)|^2\right]|\mathrm{\Phi }_G(𝑹_𝑮;t)|^2.$$
(18)
(ii) No wavepacket spreading is allowed for $`\mathrm{\Phi }_G(𝑹_𝑮;t)`$ which is localized with an envelope behaving as a $`\delta `$-like function, i.e.:

$$|\mathrm{\Phi }_G(𝑹_𝑮)|^2\delta (R_Gvt).$$
(19)
The integration over $`𝒓_\mathrm{𝟐}`$ (with $`\mathrm{d}𝒓_\mathrm{𝟐}=2\mathrm{d}𝑹_𝑮`$) finally leads to:

$$𝒋(t)=\frac{1}{mR^2}\mathrm{Im}\left[\mathrm{\Phi }^{}(𝑹;t)\frac{}{R}\mathrm{\Phi }(𝑹;t)𝒖_𝑹+imv|\mathrm{\Phi }(𝑹;t)|^2𝒖_𝒚\right]|_{𝑹=2𝒓_\mathrm{𝟏}2vt𝒖_𝒚},$$
(20)
with a rather intuitive interpretation of the two components of the flux. The first ı.e. $`\mathrm{\Phi }^{}(𝑹;t)\frac{}{R}\mathrm{\Phi }(𝑹;t)𝒖_𝑹`$ is merely the current density generated by the expanding wavepacket in the center of mass frame, whereas the second corresponds to the current associated with a density $`\frac{|\mathrm{\Phi }|^2}{R^2}`$ travelling with a velocity $`v`$ along $`𝒖_𝒚`$. The calculation can be further conducted analytically by deriving an asymptotic (i.e. $`R\mathrm{}`$, $`t\mathrm{}`$) expression for $`\mathrm{\Phi }`$ 126 . This is done using a time evolution expression involving the Fourier transform Eq.(11). Actually, one has for large $`R`$, where the potentials can be considered as constant and after the laser is turned off:

$$\widehat{\mathrm{\Phi }}(k,\theta ,\varphi ;t)=e^{ik^2t/m}\widehat{\mathrm{\Phi }}(k,\theta ,\varphi )$$
(21)
the solution being induced only by the radial part of the kinetic energy. Returning back to the wavepacket in the coordinate space:

$$\mathrm{\Phi }(R,\theta ,\varphi ;t)=\frac{1}{\sqrt{2\pi }}_{\mathrm{}}^{\mathrm{}}dk\widehat{\mathrm{\Phi }}(k,\theta ,\varphi )e^{ik^2t/m}e^{ikR}$$
(22)
and replacing $`\widehat{\mathrm{\Phi }}`$ by its expression Eq.(11), one gets:

$$\mathrm{\Phi }(R,\theta ,\varphi ;t)=\left(\frac{m}{4i\pi t}\right)^{1/2}_0^{\mathrm{}}dR^{}\mathrm{\Phi }(R^{},\theta ,\varphi )e^{im(RR^{})^2/4t}.$$
(23)
Expanding the $`R`$-dependent part of the exponential as:

$$e^{\frac{im}{4t}(RR^{})^2}=e^{\frac{imR^2}{4t}}e^{\frac{imRR^{}}{2t}}\left[1+\left(e^{\frac{imR_{}^{}{}_{}{}^{2}}{4t}}1\right)\right]$$
(24)
and observing 22  that for large $`t`$:

$$\underset{t\mathrm{}}{lim}\left|\left(e^{\frac{imR_{}^{}{}_{}{}^{2}}{4t}}1\right)\right|=0,$$
(25)
an asymptotic expression is obtained for $`\mathrm{\Phi }(R,\theta ,\varphi ;t)`$:

$$\mathrm{\Phi }(R,\theta ,\varphi ;t)_t\mathrm{}\left(\frac{m}{2it}\right)^{1/2}e^{\frac{imR^2}{4t}}\widehat{\mathrm{\Phi }}(\frac{mR}{2t},\theta ,\varphi ).$$
(26)
While recasting Eq.(26) into Eq.(20), a rather simple expression results for the asymptotic flux:

$$𝒋(t)=\frac{m}{2Rt^2}\left[𝒖_𝑹+\frac{2vt}{R}𝒖_𝒚\right]\left|\widehat{\mathrm{\Phi }}(\frac{mR}{2t},\theta ,\varphi )\right|^2|_{𝑹=2(𝒓_\mathrm{𝟏}vt𝒖_𝒚)}$$
(27)
The calculation of the projection of $`𝒋`$ on $`𝒖_𝒚`$ (cf Eq.12) requires the vector relation of Eq.(A-7) that finally leads to:

$$𝒋𝒖_𝒚=\frac{mD}{4t^2}\frac{1}{[\rho ^2+(Dvt)^2]^2}\left|\widehat{\mathrm{\Phi }}(\frac{mR}{2t},\theta ,\varphi )\right|^2.$$
(28)
where $`R`$ depends on $`t`$ as given by Eq.(A-3).

The final step is to transform the time integration of $`𝒋𝒖_𝒚`$, involved in Eq.(12), into an integration over the kinetic momentum. We proceed to a change of variable:

$$k=[\rho ^2+(Dvt)^2]^{1/2}\frac{mv}{D}=\frac{R}{2}\frac{mv}{D},$$
(29)
the physical meaning of which will be clarified hereafter. Straightforward calculations show that Eq.(29) can be inverted as:

$$t=\{\begin{array}{c}\frac{D}{v}\left(1\frac{(k^2k_\rho ^2)^{1/2}}{mv}\right)\mathrm{for}t[0,\frac{D}{v}](k[k_\rho ,(k_\rho ^2+m^2v^2)^{1/2}])\hfill \\ \frac{D}{v}\left(1+\frac{(k^2k_\rho ^2)^{1/2}}{mv}\right)\mathrm{for}t[\frac{D}{v},+\mathrm{}](k[k_\rho ,+\mathrm{}])\hfill \end{array},$$
(30)
upon the introduction of the notation

$$k_\rho =mv\frac{\rho }{D}$$
(31)
and leads to:

$$\mathrm{d}t=\frac{D}{mv^2}\frac{k}{\left(k^2k_\rho ^2\right)^{1/2}}\mathrm{d}k.$$
(32)
The $``$ signs correspond to the two time intervals depicted in Eqs(30). The time dependent argument of $`\widehat{\mathrm{\Phi }}`$ in Eq.(26) can than be expressed using the two variables $`k`$ (Eq.(29)) and $`k_\rho `$ (Eq.(31)) as:

$$\frac{mR}{2t}=\frac{m}{t}[\rho ^2+(Dvt)^2]^{1/2}=\frac{D}{vt}k=k\left(1\frac{(k^2k_\rho ^2)^{1/2}}{mv}\right)^1.$$
(33)
The experimental conditions, are such that the velocity $`v`$ of the molecular beam is much greater than the fragments relative velocity. We can thus consider $`(k^2k_\rho ^2)^{1/2}/mv`$ as negligible when compared to 1, taking into account that $`D`$ is much larger than $`\rho `$. The resulting approximation, namely:

$$t\frac{D}{v}\mathrm{a}nd\frac{mR}{2t}k$$
(34)
merely means that the time needed for a fragment to reach the pixel $`M(\rho ,\alpha )`$ is approximately the same as the one needed for the center of mass $`G`$ to reach the center $`O^{}`$ of the detector. In the framework of this approximation, the meaning of $`k_\rho =m\rho v/Dm\rho /t`$ (defined by Eq.(31) ) is also clear: i.e. the projection of the kinetic momentum $`k`$ on the detector plane. Finaly we obtain for the time integrated flux:

$$_0^{\mathrm{}}𝒋𝒖_𝒚dt=\frac{m^2v^2}{4D^2}\left[_{k\rho }^{\mathrm{}}+_{k\rho }^{(k_\rho ^2+m^2v^2)^{1/2}}\frac{\left|\widehat{\mathrm{\Phi }}(k,\theta ,\varphi )\right|^2}{k\left(k^2k_\rho ^2\right)^{1/2}}dk\right]$$
(35a)
$$=\frac{m^2v^2}{2D^2}_{k\rho }^{\mathrm{}}\frac{\left|\widehat{\mathrm{\Phi }}(k,\theta ,\varphi )\right|^2}{k\left(k^2k_\rho ^2\right)^{1/2}}dk.$$
(35b)
where the upper bond of the second integral in Eq.(35a) has been extended up to $`+\mathrm{}`$ considering that $`|\widehat{\mathrm{\Phi }}(k,\theta ,\varphi )|=0`$ for $`k>mv`$, which is equivalent to state that the center of mass kinetic momentum $`2mv`$ is much larger than the relative momentum of photofragments $`k`$. Recasting Eqs(35) in Eq.(12), taking into account cylindrical symmetry over $`\varphi `$ and calculating the pre-integral factor as:

$$\frac{m^2v^2}{D^2}\mathrm{d}S=\frac{mv\rho }{D}\frac{mv\mathrm{d}\rho }{D}\mathrm{d}\alpha =k_\rho \mathrm{d}k_\rho \mathrm{d}\alpha .$$
(36)
one finally gets:

$$\mathrm{d}N(k_\rho ,\alpha )=Nk_\rho \mathrm{d}k_\rho \mathrm{d}\alpha \frac{1}{2}_{k_\rho }^{\mathrm{}}\frac{\left|\widehat{\mathrm{\Phi }}(k,\theta )\right|^2}{k\left(k^2k_\rho ^2\right)^{1/2}}dk.$$
(37)
The dependence over $`\theta `$ of the right-hand-side of Eq.(37) has to be expressed in terms of $`\alpha `$, referring to the frame transformation Eq.(A-9)

$$\mathrm{cos}\theta =\frac{k_\rho }{k}\mathrm{cos}\alpha $$
(38)
in such a way that, ultimately $`\mathrm{d}N`$ is written only in terms of the variables $`k_\rho `$ and $`\alpha `$, with the parameters $`v`$ and $`D`$ characterizing the experimental setup:

$$\mathrm{d}N(k_\rho ,\alpha )=Nk_\rho \mathrm{d}k_\rho \mathrm{d}\alpha \frac{1}{2}_{k_\rho }^{\mathrm{}}\frac{\left|\widehat{\mathrm{\Phi }}(k,\mathrm{arccos}(k_\rho /k\mathrm{cos}\alpha ))\right|^2}{k\left(k^2k_\rho ^2\right)^{1/2}}dk.$$
(39)
The probability to record a hydrogen atom on the surface element $`\mathrm{d}S`$ (pixel $`M`$) located at $`\rho `$, $`\alpha `$ on the MCD (with a kinetic momentum $`k_\rho `$) is obtained by a proper normalization:

$$P(k_\rho ,\alpha )\mathrm{d}S=\frac{1}{N}\mathrm{d}N(k_\rho ,\alpha )=\frac{\mathrm{d}S}{2}_{k_\rho }^{\mathrm{}}\frac{\left|\widehat{\mathrm{\Phi }}(k,\mathrm{arccos}(k_\rho /k\mathrm{cos}\alpha ))\right|^2}{k\left(k^2k_\rho ^2\right)^{1/2}}dk.$$
(40)
It is interesting to note that the two probabilities $`𝒫(k,\theta )`$ (given in Eq.10) and $`P(k_\rho ,\alpha )`$ (Eq.(40)) are simply connected by:

$$P(k_\rho ,\alpha )=\frac{1}{2}_{k_\rho }^{\mathrm{}}\frac{𝒫(k,\theta )}{k\left(k^2k_\rho ^2\right)^{1/2}}dk.$$
(41)
Two remarks are in order:

i) both equations Eq.(40) and Eq.(41) involve a singularity at $`k=k_\rho `$. This difficulty can be overcame by a partial integration leading to:

$$\begin{array}{c}\hfill P(k_\rho ,\alpha )=\frac{1}{2k_\rho }\mathrm{arccos}\left(\frac{k_\rho }{k}\right)𝒫(k,\theta )|_{k=k\rho }^{k=\mathrm{}}\frac{1}{2k_\rho }_{k_\rho }^{\mathrm{}}\mathrm{arccos}\left(\frac{k_\rho }{k}\right)\frac{\mathrm{d}}{\mathrm{d}k}𝒫(k,\theta )dk\end{array}$$
(42)
The integrated term in the right-hand-side of Eq.(42) is null, due to the fact that $`𝒫(k,\theta )|_{k=\mathrm{}}=0`$. As for the total derivative with respect to $`k`$ of $`𝒫(k,\theta )`$, it results into:

$$\begin{array}{c}\hfill \frac{\mathrm{d}}{\mathrm{d}k}𝒫(k,\theta )=\frac{𝒫}{k}+\frac{k_\rho \mathrm{cos}\alpha }{k(k^2k_\rho ^2\mathrm{cos}^2\alpha )^{1/2}}\frac{𝒫}{\theta }.\end{array}$$
(43)
When recasting Eq.(43) into Eq.(42) one obtains:

$$\begin{array}{c}\hfill P(k_\rho ,\alpha )=\frac{1}{2k_\rho }_{k_\rho }^{\mathrm{}}\mathrm{arccos}\left(\frac{k_\rho }{k}\right)\left[\frac{𝒫}{k}+\frac{k_\rho \mathrm{cos}\alpha }{k(k^2k_\rho ^2\mathrm{cos}^2\alpha )^{1/2}}\frac{𝒫}{\theta }\right]dk\end{array}$$
(44)
For $`kk_\rho `$, the singularity in the coefficient of $`\frac{𝒫}{\theta }`$ may only occur for $`\alpha =0`$. This is fortunately compensated by the $`\mathrm{arccos}(k_\rho /k)`$ term of Eq.(42). Actually expanding Eq.(42) in terms of powers of $`(1k_\rho /k)`$ one ends up with a non-singular behavior, i.e. $`\frac{1}{k_\rho }\frac{𝒫}{\theta }`$ for the integrand in the vicinity of $`k_\rho `$.

ii) Despite the fact that the experimental situation we are describing is not amenable to a simple mapping on the detector plate of a photodissociation that had already occured in the center of mass frame (as a figure 1), it turns out that Eq.(40) can finally be recast in terms of the commonly used Abel transformation 225 :

$$P(k_\rho ,\alpha )=\frac{1}{4}𝒜\left[\left|\frac{\widehat{\mathrm{\Phi }}(k,\mathrm{arccos}(k_\rho /k\mathrm{cos}\alpha ))}{k}\right|^2\right],$$
(45)
where $`𝒜`$ is defined as 225 :

$$𝒜[f(k)](x)=2_x^{\mathrm{}}\frac{f(k)k}{\left(k^2x^2\right)^{1/2}}dk.$$
(46)
In connection with this, it is worthwhile considering the full Fourier transform of the wavefunction describing the relative motion (in contrast to the one carried in Eq.11):

$$\widehat{\mathrm{\Psi }}(𝒌)=\frac{1}{(2\pi )^{3/2}}d𝑹\mathrm{\Psi }(𝑹)e^{i𝒌𝑹}$$
(47)
It can be shown by following the same derivations as Eqs(21-26) 126 ; 22 , that asymptotically (i.e. for $`t+\mathrm{}`$ and $`R+\mathrm{}`$), one has:

$$\mathrm{\Psi }(𝑹;t)=\left(\frac{m}{2it}\right)^{3/2}e^{imR^2/4t}\widehat{\mathrm{\Psi }}\left(\frac{m𝑹}{2t}\right)$$
(48)
which, combined with Eqs(2 and 26), implies that:

$$|\widehat{\mathrm{\Psi }}(𝒌;t)|^2=\left|\frac{\widehat{\mathrm{\Phi }}(𝒌;t)}{k}\right|^2,$$
(49)
The probability in Eq.(45) appears now as the Abel transform of $`\left|\widehat{\mathrm{\Psi }}(k,\mathrm{arccos}(k_\rho /k\mathrm{cos}\alpha ))\right|^2`$.

### II.3 Rovibrationally averaged spectra

The probability distributions which are calculated in the previous paragraph refer to a given initial state ($`g`$, $`v`$, $`N`$, $`M_N`$) involved in the determination of $`\mathrm{\Phi }(t=0)`$ through Eq.(8) such that the quantity resulting from Eq.(45) is actually $`P_{v,N,M_N}(k_\rho ,\alpha )`$ using a full notation. An averaging over the initial ro-vibrational populations is thus required to reach the experimental spectra. As the rotational states $`N`$ are $`(2N+1)`$ times degenerated, a summation can be carried out over $`M_N`$, leading to:

$$P_{v,N}(k_\rho ,\alpha )=\frac{1}{2N+1}\underset{M_N=0}{\overset{N}{}}c_{M_N}P_{v,N,M_N}(k_\rho ,\alpha ),$$
(50)
where $`c_0=1`$ and $`c_{M_N}=2`$ (for $`M_N0`$), due to the fact that the total Hamiltonian does not depend upon the sign of $`M_N`$. The homonuclear diatomic character of H$`{}_{}{}^{+}{}_{2}{}^{}`$ implies a total wavefunction (accounting for the nuclear spin) that is antisymmetric with respect to the interchange of identical nuclei. To ensure such a property the total nuclear spin number $`T`$ must be either $`0`$ (associated with even $`N`$), or $`1`$ (associated with odd $`N`$). Due to very rare singlet ($`T=0`$) - triplet ($`T=1`$) transitions, molecular hydrogen mainly consists of two distinct species: parahydrogen ($`T=0`$) and orthohydrogen ($`T=1`$). The occurrence of ortho states is three times more probable than the para ones 14 . This nuclear spin statistics is accounted for, by a weighting coefficient $`g_N`$, affecting the rotational populations $`N`$, such that

$$g_N=\{\begin{array}{c}1\text{ for even }N\\ 3\text{ for odd }N\end{array}$$
(51)
Apart from this factor, rotational populations are also thermally weighted, according to a Boltzman distribution described by a rotational temperature $`T_v`$ depending on the initial vibrational level. The weighting coefficient is given by:

$$b_N=\mathrm{exp}\left[\frac{\mathrm{\Delta }E(v,N)}{k_\beta T_v}\right].$$
(52)
where $`k_\beta `$ stands for the Boltzman constant and $`\mathrm{\Delta }E(v,N)`$ for the rotational energies resulting from the solution of Eq.(9):

$$\mathrm{\Delta }E(v,N)=E(v,N)E(v,0).$$
(53)
The rotationally averaged probabilities resulting from these considerations are

$$P_v(k_\rho ,\alpha )=\frac{1}{Q_v}\underset{N}{}b_Ng_NP_{v,N}(k_\rho ,\alpha ),$$
(54)
where $`Q_v`$ is a normalization factor:

$$Q_v=\underset{N}{}b_Ng_N.$$
(55)
The comparison with experimental spectra has also to take into account initial vibrational populations $`a(v)`$ (i.e. as they result from the electric discharge acting over H2, prior to the laser excitation):

$$P(k_\rho ,\alpha )=\frac{1}{Q}\underset{v}{}a(v)P_v(k_\rho ,\alpha ),$$
(56)
with

$$Q=\underset{v}{}a(v).$$
(57)
We note that the informations concerning the initial vibrational distribution $`a(v)`$ as well as the corresponding rotational temperature $`T_v`$, have to be provided by experimental measurements.

### II.4 Laser spatial intensity averaging

Although particular attention is devoted in the experimental measurements for obtaining a well focussed ion beam, the molecules are actually excited by different field amplitudes according to their positions ($`x`$, $`y`$), due to a non-homogeneous spatial intensity distribution $`I(x,y)`$ in the laser beam. It turns out that an average over these non-homogeneities has a basic importance when attempting a quantitative interpretation of experimental data, as will be clear in the next section. The average implies a double spatial integration over the variables $`x`$ and $`y`$ (see figure 6):

$$P(k_\rho ,\alpha )=_L^L𝑑x_{\mathrm{}}^+\mathrm{}P(k_\rho ,\alpha ;I(x,y))𝑑y.$$
(58)
$`x`$ being limited to a finite interval $`2L`$ measuring the width of the ion beam. The integrand itself is nothing but the probability calculated in Eq.(56) with as an additional argument the intensity $`I(x,y)`$, for which this probability is calculated, i.e. $`P(k_\rho ,\alpha ;I(x,y))`$. For parity reasons Eq.(58) may be also written as:

$$P(k_\rho ,\alpha )=4_0^L𝑑x_0^+\mathrm{}P(k_\rho ,\alpha ;I(x,y))𝑑y.$$
(59)
A gaussian shape is assumed for the 2D behavior of the laser within its focus area:

$$I(x,y)=I_0\mathrm{exp}\left[\frac{x^2}{r_x^2}\right]\mathrm{exp}\left[\frac{y^2}{r_y^2}\right]$$
(60)
where $`r_x`$ and $`r_y`$ are the radii of the focal area, such that $`I(r_x,r_y)=I_0/e^2`$. These parameters are obtained from the experimental setup 12  as:

$$r_{x,y}=\frac{\lambda f}{2\pi b_{x,y}}$$
(61)
where $`\lambda `$ is the laser wavelength and $`f`$ is the focal length of the parabolic mirror focusing the laser beam. $`b_x`$ and $`b_y`$ correspond to the extensions in each direction $`x`$ and $`y`$ where 50% of the energy is dissipated. The peak intensity is calculated whence the total pulse energy $`E_0`$ and an autocorrelation time $`t_{ac}`$ have been measured:

$$I_0=\frac{2\sqrt{2\mathrm{ln}2}E_0}{\pi ^{3/2}r_xr_yt_{ac}}.$$
(62)
The double integration involved in Eq.(59) can be conducted, by integrating first over $`y`$, referring to a variable change:

$$y=r_y\left[\mathrm{ln}\left(\frac{I}{I_x}\right)\right]^{1/2}$$
(63a)
$$dy=\frac{r_y}{2}\left[\mathrm{ln}\left(\frac{I}{I_x}\right)\right]^{1/2}\frac{dI}{I},$$
(63b)
where $`I_x=I_0\mathrm{exp}\left[(x/r_x)^2\right]`$. The result is:

$$P(k_\rho ,\alpha ;I_x)=2r_y_0^{I_x}\frac{P(k_\rho ,\alpha ;I)}{I\left[\mathrm{ln}\left(\frac{I}{I_x}\right)\right]^{1/2}}𝑑I.$$
(64)
Two singularities affect such an expression; namely at $`I=0`$ and at $`I=I_x`$. The first has no consequence, as for $`I=0`$, $`P(k_\rho ,\alpha ;I=0)=0`$. The second can be avoided when integrating by part:

$$P(k_\rho ,\alpha ;I_x)=2r_y\left[2\sqrt{I/I_x}P(k_\rho ,\alpha ;I)+_0^{I_x}2\sqrt{I/I_x}\frac{d}{dI}P(k_\rho ,\alpha ;I)𝑑I\right]$$
(65)
An identical procedure is then applied for the second integral over $`x`$. The final result is

$$P(k_\rho ,\alpha )=2r_x\left[2\sqrt{I_x/I_0}P(k_\rho ,\alpha ;I_x)|_{I_x=I_L}^{I_x=I_0}+_{I_L}^{I_0}2\sqrt{I_x/I_0}\frac{d}{dI_x}P(k_\rho ,\alpha ;I_x)𝑑I_x\right]$$
(66)
where $`I_L`$ is the field intensity at ($`x=L`$, $`y=0`$).

## III Results

This section presents the results of the simulation and interpretation of experimental data. Among the experimental results obtained in H.Figger’s group 12 ; 20 ; 21  three are retained. The laser intensities $`I_0`$ have been slightly adjusted with respect to laboratory measurements of the total pulse energy $`E_0`$ and autocorrelation time $`t_{ac}`$, to fit experimental spectra. The resulting parameters are collected in Table 1. The laser pulse carrier wavelength is $`\lambda `$=785 nm.

In the calculations the intensity spatio-temporal distribution is assumed to be:

$$I(x,y;t)=I_0\mathrm{exp}\left[\frac{x^2}{r_x^2}\right]\mathrm{exp}\left[\frac{y^2}{r_y^2}\right]\mathrm{exp}\left[\frac{2t^2}{w_t^2}\right]$$
(67)
with the relations between the parameters as given by Eqs(61, 62). The widht of the molecular jet is $`L`$=50 $`\mu `$m, its velocity is $`v`$=106 m/s and focal area parameters values are $`b_x`$=2.6 mm, $`b_y`$=2.4 mm, $`f`$=1000 mm, resulting into $`r_x`$=48$`\mu `$m, $`r_y`$=52$`\mu `$m. In the calculations described below the parameter $`w_t=t_{ac}/2\sqrt{ln2}`$, which define the laser pulse temporal shape, have been taken equal to 140 fs.

Figure 3 displays three-dimensional representations of the dissociation probabilities as a function of their angular ($`\alpha `$) and kinetic ($`k_\rho `$) distributions. The upper diagram corresponds to the experimental results $`P^e`$ 20  for the laser excitation parameters indicated on the last row of Table 1. The lowest two diagrams give the calculated spectrum ($`P^c`$) and the absolute value of the difference $`\left|P^eP^c\right|`$, for the same laser characteristics, at the same scale. The normalization is such that:

$$_0^{\mathrm{}}k_\rho 𝑑k_\rho _0^{\pi /2}P^{e,c}(k_\rho ,\alpha )𝑑\alpha =1.$$
(68)
The successive peaks that are obtained correspond to photofragments arising from different vibrational levels $`v`$ of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$. The energies of the levels are positioned in figure 4 on the rotationless dressed molecular potentials resulting from the diagonalization of the radiative interaction at fixed angle $`\theta =0`$.

The most important peak (at $`\alpha =0`$) corresponds to $`v`$=7 and is followed in decreasing order by the peaks assigned to $`v`$=8,9,10. The peak resulting from the dissociation of $`v`$=6, with a much smaller contribution is hidden by the peak $`v`$=7, whereas those resulting from $`v`$=11,12 are in the blue-wing of $`v`$=10. It is interesting to note that, on the lowest diagram, the largest error affects the peak resulting from v=9, all others being well represented. This is to be relationed with the particular energy of $`v`$=9 (see figure 4) very close to the avoided crossing of the dressed potentials. The characteristics of this region being very sensitive to the laser spatial and temporal intensity distributions, even small deviations with respect to experimental evaluations may lead to appreciable differences explaining figure 3(c).

In figure 5 we show the four main steps to obtain the photofragments distribution Pc, which may be compared with the experimental one. On each step we plot the cut of the resulting distribution at $`\theta =0`$ for $`𝒫(k,\theta )`$, or $`\alpha =0`$ for $`P(k_\rho ,\alpha )`$. The upper panel gives the photodissociation probabilities starting from individual vibrational levels of H$`{}_{}{}^{+}{}_{2}{}^{}`$, as calculated in the molecular frame for $`\theta `$=0 and as a function of $`k`$, for laser characteristics corresponding to the last row of Table 1. The vertical lines illustrate the theoretical energies of the vibrational levels of H$`{}_{}{}^{+}{}_{2}{}^{}`$ in a field-free situation. As expected, from the examination of figure 4, the maxima of the peaks with $`v<9`$ are shifted down and these of $`v>9`$ are shifted up, due to the radiative coupling. As to the height of the successive peaks, a decrease from $`v`$=6 to $`v`$=9 is observed. This, however, does not mean that $`v`$=9 is less dissociated than $`v`$=6, as the information which is displayed concerns a cut at angle $`\theta =0`$.

The major effect, when attempting a theory-versus-experiment comparison, is the role played by the spatial intensity distribution of the laser, that so far, has been neglected by referring to the large laser focal area with respect to the diameter of the ion beam Kondorskiy . Spatial averaging brings into interplay molecules interacting with radiative fields having intensities less than the maximum value $`I_0`$. This may lead to very large effects on some vibrational levels as is seen in figure 5 panel (b). More precisely, the peak associated with $`v`$=6 is nearly washed out, whereas those describing photodissociation starting from $`v`$=9 and $`v`$=11 seem to be enhanced. Only the laser maximum intensity leads to a barrier lowering (bond softening) mechanism for $`v`$=6. When a spatial average is carried out, with the inclusion of lower intensities, the photodissociation from $`v`$=6 is severely inhibited due to very low tunneling, which explains the flat behavior of $`𝒫_v^i(k)`$ for $`v`$=6.The vibrational states $`v`$=7,8 are also affected by this effect but in a lesser extend as they are closer to the top of the lower adiabatic potential barrier. The level $`v`$=9 is again in a particular situation, energetically lying on the very top of the barrier. In other words, its photodissociation is not inhibited by any spatial intensity averaging, and this is why it leads to a narrower and higher peak, than the ones originating from $`v`$=7,8. The narrowing of the peak, in particular, is in relation with the fact that only a limited energy range corresponds to efficient dissociation within the open gate between the lower and upper adiabatic potentials that gets narrower with decreasing intensities. The behavior of $`v`$=11 deserves particular interest, as its photodissociation is rather through a vibrational trapping mechanism involving the upper adiabatic potential. Lower the field intensity and lesser is the efficiency of this trapping. The spatial intensity averaging of the laser leads as a consequence to better relative dissociation from $`v`$=11 resulting into a high peak.

Figure 5 panel (c) displays the dissociation probabilities $`P_v^a(k_\rho )`$ as functions of $`k_\rho `$ after the Abel transformation Eq.(41). The basic difference with $`𝒫_v^i(k)`$ (panel b) is the rise of long range red tails of the individual peaks, especially for $`v9`$. This is due to the nonlinear features of the Abel transformation, mixing up a whole range of $`\theta `$-dependent probabilities for a single $`\alpha `$. Less aligned fragment distributions resulting from $`v`$=9,10,11 present tails that are much more marked than the ones coming from $`v`$=7 and 8.

The following step for building the experimental observable is the convolution with the detector resolution window which is taken as a square gate of 0.07 a.u. in kinetic momentum units, corresponding approximately to a pixel size of 70 $`\mu m`$. This as expected, results into the smoothing of very sharp structures such as the peaks associated with $`v`$=9 and 11 (pannel d).

Finally the theoretical spectrum is obtained as a sum of partial vibrational distributions with weights corresponding to the vibrational populations as given by Eqs(56-57). Panel (e) of figure 5 displays the resulting kinetic energy spectrum which is directly compared with the experimental one. An excellent agreement is obtained, the most noticeable differences occurring in the vicinity of $`v`$=9, which corresponds to an energy region particularly sensitive to possible inaccuracies related with the spatial intensity averaging of the laser.

The information we get from figure 5 can be summarized as follows: apart from the geometrical Abel transformation which is needed to bridge the dissociation probabilities evaluated in the ($`k`$-$`\theta `$) frame, to the photodissociation spectra as recorded on the detector plate, one has to take into consideration basically two additional facts, when attempting a quantitative interpretation of the experimental data:

i) The first is the spatial intensity distribution of the laser. Figure 6 displays a three-dimensional view of the relative spatial extensions of the laser focal area and that of the molecular beam as is actually the case in the experiments. Clearly, all the molecules are not subjected to the same intensity at a given time, requiring thus a spatial averaging, the role of which is one of the most striking.

Figure 7 gathers the spectra on the detector plate, for $`\alpha =0`$ and as a function of $`k_\rho `$ for two models: namely, with and without the spatial averaging over the laser intensity distribution. The results are compared to the experimentally recorded data. A huge decrease affects the spectrum in the momentum region extending from $`k_\rho `$ 3 to 5 a.u. when averaging over the field intensities. This precisely corresponds to the contributions of vibrational levels $`v`$=6,7 well protected against potential barriers that are high for lower intensities taking part in the averaging process. Thus the spatial averaging turns out to be crucial when comparing with experimental spectra.

ii) The second is an accurate knowledge of the field-free vibrational populations of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$, which take part in Eq.(56) through the function $`a(v)`$. Figure 8 displays in terms of histograms the relative vibrational populations of levels $`v`$=6,…,12 as they result from an estimation based on similar discharge experiments 21 . They are actually subjected to errors presumably within 10 to 15% in relative values.

A calculation based on them leads to the spectrum illustrated in figure 9 which basically disagrees with the experimental one over a region close to $`k_\rho `$ 5 to 6 a.u., corresponding to the most important peak. However, a nice agreement is obtained after some small modifications of the vibrational populations, not exceeding reasonable error bar limits and remaining within the overall decreasing behavior for high $`v`$’s, as is plotted in figure 8. It is worthwhile noting that this adjustment is done once for all, for given laser parameters (0.7 mJ of total energy) and is used hereafter for all other theory-versus-experiment comparisons.

The spectra are gathered within the frame of two one-dimensional representations: either as a function of the kinetic momentum $`k_\rho `$ or as a function of the angle $`\alpha `$ on the detector. Figure 10 gives the cuts (at $`\alpha `$=0) as a function of $`k_\rho `$, for three laser fields, whose characteristics are precisely the ones indicated on Table 1. It might be noted here that peak intensity value $`I_0`$ calculated using Eq.(62) strongly depends from the experimentaly measured parameters $`b_x`$, $`b_y`$ and $`E_0`$. In third column of Table 1 we give the intensities corresponding to the best agreement between experimental and calculated spectra presented on figure 10. This adjustment is necessary to reproduce correctly the left part of the spectra, which is particularly sensitive to the laser intensity, as can be seen in figure 7. We emphasized that this adjustment has only been performed for one-dimensional spectra corresponding to ($`\alpha `$=0). For the same pulse duration the laser intensities are ranging from low to medium and strong, following the panels a,b, and c. Three features can be emphasized:

i) Three major peaks are obtained, corresponding to the dissociation involving $`v`$=7, 8 and 9 levels, positioned in this order in the region $`k_\rho `$ 5 to 8 a.u. The theory-experiment agreement is good not only for the positions but also for the relative heights of these peaks; the most noticeable difference affecting again $`v`$=9, more sensitive to an accurate evaluation of the spatial intensity distribution;

ii) The strongest field (E0=0.7 mJ, panel c) reveals the rise of an additional peak at the position of $`v`$=6. This is related with the bond softening mechanism, where the radiative coupling induces an important adiabatic barrier lowering, large enough for the population initially in the bound state $`v`$=6 to escape through tunneling. Excellent agreement with experimental results is obtained for this bump in the spectrum ;

iii) The blue tail of the spectrum extending above $`k_\rho `$ 8 a.u. corresponds to the photodissociation of initial populations on $`v`$=10,11 and 12, which due to possible vibrational trapping effects, is less efficient. Here again excellent theory-experiment agreement is reached.

The angular distributions for the same field characteristics, are gathered in figure 11. They, precisely, correspond to $`\alpha `$-dependent 1D representations of fixed $`k_\rho `$-cuts of the 3D information of the type displayed in figure 3. This is done for two different values of $`k_\rho `$; namely $`k_\rho `$=5.5 a.u. and $`k_\rho `$=6.5 a.u. corresponding to the positions of the maximum amplitudes of the two major peaks of figure 10 attributed to $`v`$=7 and 8, respectively. The following observations can be pointed out:

i) These angular distributions, although labeled as $`v`$=7 and 8, actually contain informations originating from $`v`$=9,10,…, through the red-tail contributions of these levels (as is clear from figure 5 panel c). The excellent theory-versus-experiment agreement that is reached has to be judged within this intricate influence of the higher energy part of the spectrum. It is also worthwhile noting that due to larger experimental errors affecting $`v`$=9,10, angular distributions are not studied for higher $`v`$’s than 8.

ii) $`v`$=7 is much better aligned than $`v`$=8. This is basically due to the bond softening mechanism. A high potential barrier at $`\theta =\pi /2`$ protects $`v`$=7 population against photodissociation. This barrier is lowered at $`\theta `$=0 or $`\pi `$ where the radiative coupling is at its maximum, leading to efficient alignment, that is even better for increasing intensity. In other words the wavepacket associated with $`v`$=7 has to skirt around a high potential barrier at $`\theta =\pi /2`$ before dissociating, whereas the one associated with $`v`$=8 being closer to the top of the barrier can more easily tunnel. The consequence is that dissociation is facilitated for $`\theta `$=0, or $`\pi `$, when the initial population lies on $`v`$=7.

A better understanding and interpretation of the way following which these complementary bound softening and vibrational trapping mechanisms ultimately affect the dissociation process, could be gained by a dynamical investigation. Figure 12 illustrates a time-resolved decay dynamics of individual vibrational levels. The lower panel gives the temporal shape of the laser intensity for the strongest field into consideration (E0=0.7 mJ, with the parameters of the last row of Table 1). The decay dynamics is given in terms of the decrease of the short range population as a function of time, starting from a given $`v`$ of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$ (i.e. the time dependence of the norm of the internal region wavepacket $`\mathrm{\Phi }^I^2`$, as defined in subsection 2.1). The behavior of different $`v`$’s can be classified as follows:

$``$ Levels affected by the bond softening mechanism; namely $`v`$=6,7,8. The decay starts only after the maximum of the laser pulse, which is required for the potential barriers to be sufficiently lowered. Although the decay mechanism is rather fast (the slope of $`\mathrm{\Phi }^I^2`$ versus time is large), the photodissociation starting from $`v`$=6 is not complete, due to the fact that the potential barrier is closed before total escape towards the asymptotic region.

$``$ $`v`$=9 which lies at the curve crossing region dissociates completely and faster than all other levels;

$``$ Levels affected by the vibrational trapping mechanism; namely $`v`$=10,11,12. The populations of these levels start to dissociate during the laser rise time, but about the maximum intensity their decay rate is lowered (the slope of $`\mathrm{\Phi }^I^2`$ versus time lower than the one of levels $`v`$=6,7,8). This is basically due to the fact that they are vibrationaly trapped in the temporarily closed upper adiabatic potential. It is also interesting to note that the population of $`v`$=12, trapped during the radiative interaction, partially returns back to the ground state bound potential, in such a way that dissociation starting from $`v`$=12 is not complete.

The dynamical alignment characteristics are illustrated in figure 13. Here again the lower panel indicates the temporal shape of the strongest laser. The upper panels display the average value of $`\mathrm{cos}^2\theta `$ on the internal region wavepacket; i.e. $`\mathrm{\Phi }^I|\mathrm{cos}^2\theta |\mathrm{\Phi }^I/\mathrm{\Phi }^I|\mathrm{\Phi }^I`$, indicating the alignment characteristics of the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$ as a function of time. Three initial levels are in consideration, each pertaining to one of the previously selected classes. The bond softening mechanism leading to the dissociation of $`v`$=6 (panel a) results into very efficient alignment during the pulse, which even remains during the fall off regime.

A thorough interpretation, already given in the literature 24 , can be summarized by referring to a three dimensional representation of the adiabatic potential energy surfaces (displayed in figure 4). This is provided in figure 14 for a single photon dressed ground and excited states of H$`{}_{}{}^{+}{}_{2}{}^{}`$ including (by diagonalization) the radiative interaction. The photodissociation dynamics starting from $`v`$=6 is described by a wavepacket that evolves on the lower adiabatic potential surface. It has first to skirt around the potential barrier at $`\theta =\pi /2`$ and end up in the lower energy valley at $`\theta =0`$ or $`\pi `$. This is why fragments originating from a parent ion in an initial state well protected by a hardly penetrable potential barrier (as for $`v`$=6,7,8) are well aligned through the bond softening mechanism. On the opposite situation are parent ions in an initial state basically pertaining to the upper adiabatic potential energy surface (as for $`v`$=10,11,12). This surface presents a minimum around $`\theta =\pi /2`$, where the population is temporarily trapped. The dissociation by a single photon absorption further proceeds by a non-adiabatic transition to the lower adiabatic surface. Such a transition is more efficient for $`\theta \pi /2`$ (induced by a lower radiative coupling). Although the last step which is the evolution on the lower adiabatic surface tends to align the fragments, this effect is less efficient as the parent ion is prepared at $`\theta \pi /2`$ on this surface. The result is clearly understandable in terms of this vibrational trapping mechanism for $`v`$=12 (panel c, figure 13). During the rise time of the laser pulse, the parent ion is well trapped on the upper adiabatic surface leading to a misalignment (the bump of the $`\mathrm{cos}^2\theta `$ curve at about $`t`$=550 fs). There is no noticeable alignment during the whole duration of the pulse. A second misalignment, probably due to the nonadiabatic jump, is obtained at $`t`$=800 fs. Finally $`v`$=9 which is basically not affected neither by bond softening, nor by vibrational trapping, does not show any alignment characteristics as is clear from panel b.

## IV Conclusion

Once the competition between multiphoton ionization and dissociation processes is discarded by preparing the parent ion H$`{}_{}{}^{+}{}_{2}{}^{}`$ through an electric discharge experiment, a rather simple and complete quantum modelisation is provided for a theory-versus-experiment comparison of angularly resolved kinetic energy spectra of photofragments resulting from intense field dissociation. An Abel transformation relates the probability $`𝒫(k,\theta )`$ for a single H$`{}_{}{}^{+}{}_{2}{}^{}`$ molecule in a given initial ro-vibrational state, to dissociated with kinetic momentum $`k`$ along its polar direction $`\theta `$ with respect to the laser polarization vector, to $`P(k_\rho ,\alpha )`$, the probability for the photofragment H to be detected on a pixel of the detector plate labeled by its polar coordinates ($`\rho ,\alpha `$), A quantitative reproduction of experimental data requires some statistics over initial ro-vibrational states on one hand and over the spatial distribution of laser intensities interacting with molecules positioned at different places in the ionic beam, on the other hand.

An excellent agreement is obtained with experimental spectra and especially for the alignment characteristics of the photofragments. A thorough interpretation can be conducted for single vibrational peaks of the spectra in terms of basic mechanisms, such as bond softening and vibrational trapping. The most striking observation is the major role the laser volume effect is playing, in particular over lower vibrational levels.

Among our feature prospects, is the elucidation of the role of isotope effects in the photodissociation of D$`{}_{}{}^{+}{}_{2}{}^{}`$ and HD+, which are currently studied in H.Figger’s group.

## Acknowledgements

The authors are indebted to Prof. Hartmut Figger (Max-Planck-Institut für Quantenoptik, Garching) for very fruitful discussions and for communicating them recent and unpublished spectra. We acknowledge computation time from Institut du Développement et des Ressources en Informatique Scientifique (IDRIS, CNRS).

## Appendix

This appendix is devoted to some geometrical and and vector relations illustrated in figure 2. $`𝒓_\mathrm{𝟏}`$ and $`𝒓_\mathrm{𝟐}`$ are the vectors pointing H and H+ in the laboratory frame, $`𝑹`$ and $`𝑹_𝑮`$ defined by

$$𝑹=𝒓_\mathrm{𝟏}𝒓_\mathrm{𝟐}$$
(A-1)
$$𝑹_𝑮=vt𝒖_𝒚=\frac{1}{2}(𝒓_\mathrm{𝟏}+𝒓_\mathrm{𝟐})$$
(A-2)
are the relative internuclear separation and the position of the center of mass $`G`$, respectively (by neglecting the contribution of the electron). The right-angle triangles $`OO^{}M`$ and $`O^{}M^{}M`$ lead to:

$$\frac{1}{2}𝑹^2=\rho ^2+(Dvt)^2$$
(A-3)
and

$$𝒓^2=\rho ^2+D^2$$
(A-4)
whereas from the triangle $`MGO`$ one gets:

$$\frac{1}{2}𝑹=𝒓𝑹_𝑮.$$
(A-5)
The unitary vector $`𝒖_𝑹`$ along $`𝑹`$, can be easily evaluated using Eqs(A-2,A-3) and Eq.(A-5):

$$𝒖_𝑹=\frac{𝑹}{𝑹}=\frac{𝒓vt𝒖_𝒚}{\left[\rho ^2+(Dvt)^2\right]^{1/2}}$$
(A-6)
and its projection over $`𝒖_𝒚`$ is nothing but:

$$𝒖_𝑹𝒖_𝒚=\frac{𝒓𝒖_𝒚vt𝒖_𝒚^2}{\left[\rho ^2+(Dvt)^2\right]^{1/2}}=\frac{Dvt}{\left[\rho ^2+(Dvt)^2\right]^{1/2}}$$
(A-7)
taking into account: $`𝒓𝒖_𝒚=D`$.

The polar angles $`\theta `$ and $`\alpha `$ positionning H (and $`M`$) in the center of mass and detector frames can be related using the right-angle triangle $`GM^{}M`$:

$$\mathrm{cos}\theta =\frac{HH^{}}{\frac{1}{2}𝑹}=\frac{\rho \mathrm{cos}\alpha }{\frac{1}{2}𝑹}$$
(A-8)
or finally taking into account Eq.(A-3):

$$\mathrm{cos}\theta =\frac{\rho \mathrm{cos}\alpha }{\left[\rho ^2+(Dvt)^2\right]^{1/2}}.$$
(A-9)


format: text

text:
# Influence of the cooling rate on low-temperature Raman and infrared reflection spectra of partially deuterated 𝜅-(BEDT-TTF)2Cu[N(CN)2]Br

## I Introduction

$`\kappa `$-(BEDT-TTF)2Cu\[N(CN)2\]Br \[BEDT-TTF denotes bis(ethylenedithiolo)tetrathiafulvalene\] is one of the most well-known organic superconductors.Lang and Mueller  Still, a number of issues related to its physical properties remain unclear, including the nature the superconducting state. This compound lies on the border between metals and insulators and, below 50 K, regions of an antiferromagnetic insulating phase appear inside its mostly metallic volume. Upon deuteration, the amount of the insulating phase gradually increases with increasing deuterium content.Taniguchi et al. (1999) There exists a set of progressively deuterated isotopic analogues of $`\kappa `$-(BEDT-TTF)2Cu\[N(CN)2\]Br, which are denoted as d\[n,n\] with n = 0, 1, 2, 3, or 4 being the number of deuterium atoms at both ends of a BEDT-TTF molecule.Kawamoto et al. (1998) The last member of this sequence, d, is mostly insulating at low temperatures. The cooling rate is another important factor affecting the phase separation: the faster the cooling the larger is the amount of the insulating phase.Taniguchi et al. (1999) It is believed that influence of the cooling rate on phase separation is related to ordering of ethylene groups of BEDT-TTF molecules, taking place approximately from 140 down to 50 K as a glass transition.Saito et al. (1999); Akutsu et al. (2000); Stalcup et al. (1999) Fast cooling freezes the disorder in ethylene groups, more effectively in heavier deuterated ones. The mechanism of the effect of ethylene-group disorder on phase separation is not understood in detail at the moment. A disorder of ethylene groups probably results in disorder of transfer integrals.Muller et al. (2002) Yoneyama et al.Yoneyama et al.  suggested that the disorder in ethylene groups decreases inhomogeneously upon cooling, with the formation of domains having some amount of disorder and domains that are free of disorder. The former then become insulating and the latter become metallic.

Most of experimental studies carried out so far deal with d. d is less investigated, and few works are devoted to partially deuterated crystals. At the same time, the superconductiong/insulating phase transition in d and d can be easier controlled by cooling rate.Taniguchi et al. (1999)

In our previous publication,Maksimuk et al. (2001) we reported polarised Raman spectra of $`\kappa `$-(BEDT-TTF)2Cu\[N(CN)2\]Br along with its several isotopic analogues and discussed the splittings of $`\nu _2`$ and $`\nu _3`$ molecular modes. Here, we present the cooling-rate and temperature dependences of Raman and IR spectra of d, d, d, and d single crystals in the frequency range corresponding to C=C stretching modes. We supposed that the cooling rate should have significant influence on the phonon spectra; however, only rather small effects were observed. Below we report and discuss these findings.

## II Experimental

The experimental procedure was the same as in Ref. Maksimuk et al., 2001. The crystals were grown by a standard electrochemical oxidation. The Raman spectra were measured in the back-scattering geometry by a Renishaw Ramascope System-1000 spectrometer. A 514-nm argon laser was used for excitation. The laser power on the sample surface was $``$ 50 $`\mu `$W, the spot diameter being $``$ 5 $`\mu `$m. The typical time of one measurement was 15 min. The experimental error of a wavenumber absolute value was 1 cm-1, the error of relative wavenumber shift was 0.1 cm-1, the width of the instrument response function was 3.3 cm-1.

The polarised reflection spectra in 600–4000 cm-1 region were obtained with a FT-IR Nicolet Magna 760 spectrometer combined with a Spectratech IR-Plan microscope. The spectral resolution was 4 cm-1.

Samples were held inside a helium-flow Oxford CF1104s cryostat. The sample was fixed to the holder by a small amount of the silicone grease. The temperature was monitored by a silicon diode sensor attached inside the holder just below the sample crystal.

To obtain temperature dependences the following number of different samples shown in parentheses were used: for IR measurements, d (1), d (1), d (1); for Raman measurements, laser polarisation $`𝐜`$, d (2), d (2), d (3), d (1); for Raman measurements, laser polarisation $`𝐛`$, d (2), d (1), d (1), d (1). For Raman measurements we used different samples in $`𝐜`$ and $`𝐛`$ polarisations. Several more samples of each sort were used for a rough check of the sample-to-sample spectra variations.

To obtain the parameters of separate lines, the least-square fitting by Lorentz functions was used. For each mode $`\nu `$ the position $`\omega (\nu )`$, the width $`\delta (\nu )`$ and the integrated intensity $`I(\nu )`$ were extracted. Below we will somewhere designate the laser polarisation and the type of the crystal in parentheses; for example, $`\omega (\nu _2,𝒃,2)`$ means the position of $`\nu _2`$ mode for d crystal and $`𝐛`$ laser polarisation. The polarisation of the scattered light was not analysed, so only the polarisation of the laser radiation is indicated.

At any temperature, all spectral lines could be fitted quite well except their wings. When a weak line is located near an intense one, the width of the former is influenced by the latter. For that reason, we used different laser polarisation for different modes to obtain temperature dependences.

## III Results and discussion

In Fig. 1, the Raman spectra of d in the region of C=C stretching vibrations are shown for different polarisations of the laser. The $`\nu _3`$ molecular mode gives rise to two components: $`\nu _3(A_g+B_{1g})`$ near 1475 cm-1 and $`\nu _3(B_{2g}+B_{3g})`$ near 1415 cm-1; the splitting between them is determined by the dimer–dimer electron molecular vibration (EMV) interaction.Maksimuk et al. (2001) The line originating from the mode $`\nu _2`$ appears near 1500 cm-1. The line near 1465 cm-1 was identified by us as $`\nu _{27}`$ or a combination.Maksimuk et al. (2001)

We found certain cooling-rate dependences for d and d. For d and d no dependences were found. We used ”fast” and ”slow” cooling procedures. ”Fast” cooling means approximately 20 K/min which was at the limit of the equipment used. We tried different ”slow” cooling procedures: (I) approximately 0.3–1 K/min cooling in some temperature range between 50 and 150 K, (II) annealing at some constant temperature between 60 and 80 K, (III) some combination of 0.3–1 K/min cooling and annealing.

The results obtained with d crystals showed strong variation from sample to sample. In some of the samples we could see cooling rate dependence, in others we could not. The results depended also on the way the sample was fixed. As a rule, simply after removing the sample from the holder, cleaning it from silicone grease by a solvent, and reattaching it by another small portion of grease, results different from initial ones were obtained. During the cooling the samples could jump or rotate a little if the amount of the grease was was insufficient. By this reason we could not totally remove the influence of grease. However, if the sample position remained stable, the results for this particular sample were reproducible from cooling to cooling. At low temperatures, $`\nu _2`$ and $`\nu _3`$ lines looked additionally split. We can not characterise the cooling rate dependence for d in general. However, in Fig. 2 we present the results for one specific d crystal with the biggest difference between ”slow” and ”fast” cooling — first, as an example, and second, because we used these data to estimate the overheating of the sample in the laser spot.

For Fig. 2 ”slow” cooling sequence was the following: cooling to 75 K, 1 hour annealing, 0.3 K/min cooling to 70 K, 4 hours annealing, 0.3 K/min cooling to 60 K, 1 hour annealing, 0.3 K/min cooling to 50 K, and cooling to 5 K. (The results obtained are shown by squares.) Quite different dependence was obtained upon ”fast” cooling, with most striking difference observed between 10 and 20 K; being rather unusual these results were, however, reproducible from one cooling cycle to another. To check the laser overheating we performed these measurements upon ”fast” cooling under two levels of laser power: 15 $`\mu `$W (shown by dark circles in Fig. 2, accumulation time 30 min), and 50 $`\mu `$W (shown by crosses, accumulation time 15 min).

As one can see in Fig. 2, the data for the linewidth and the splitting do not depend on the laser power allowing us to estimate that, near 10–20 K, the overheating did not exceed 3 K. We also tried to measure the overheating by another method: we increased laser power 3 times (up to about 150 $`\mu `$W), measured the signal at 90 K and estimated the overheating by change of the width and the position of $`\nu _2`$, $`\nu _3`$, and 1465-cm-1 line. Estimations based on different parameters gave different values of the overheating, however, all being between 10 and 50 K (i. e., 3–15 K for our normal laser power).

We cannot state for sure that, at nominal 5 K, the crystals were really below the critical temperature of the superconducting transition. Several measurements with d and d crystals at 5 K upon ”fast” cooling were carried out at lowered laser intensity, and no essential changes in any spectral parameter in comparison to the case of normal laser intensity were observed; however, we have very little statistics for such measurements.

d, d, d crystals showed no evident variation from sample to sample. We attached several d samples to the holder, and these samples underwent the same cooling procedure. The results were very close. Thus we can speak about the behaviour of d after ”fast” or ”slow” cooling in general.

It is worth mentioning that we did not see any considerable difference between different places of the same sample in any of d, d, d, d crystals.

The temperature dependences of $`\delta (\nu _2,𝒄)`$ and $`\delta (\nu _3(A_g+B_{1g}),𝒃)`$ are shown in Fig. 3 and Fig. 4, respectively. For d crystals $`\nu _2`$, $`\nu _3`$ modes are split.Maksimuk et al. (2001) We designate the components of these doublets as $`\nu _2^l`$, $`\nu _2^h`$, $`\nu _3^l`$, $`\nu _3^h`$. The linewidths of all components are shown in upper panels of Fig. 3 and 4 together with $`\delta (\nu _2,4),\delta (\nu _3,4)`$. Below 20–40 K $`\delta (\nu _2^l,0)`$ decreases with decreasing temperature but $`\delta (\nu _2^h,0)`$ increases.

Above 20–40 K the data for d, d, d coincide, the linewidths increasing linearly with the increase of the temperature with the slope $`(1.9\pm 0.1)\times 10^2cm^1K^1`$ for $`\delta (\nu _3)`$ and $`(2.5\pm 0.2)\times 10^2cm^1K^1`$ for $`\delta (\nu _2)`$. At low temperature $`\delta (\nu _2)`$ is about 1–2 cm-1 larger than $`\delta (\nu _3)`$. Below 20–40 K, the temperature dependences of the linewidth no longer coincide for the samples with different deuteration.

For d the cooling rate influences the result. After ”slow” cooling (open diamonds) the linewidth remains constant, after ”fast” cooling it increases with decreasing temperature. Crosses in Figs. 3 and 4 represent the data obtained when, to make a measurement in a region 50–150 K, we interrupted the ”slow” cooling procedure. Above 150 K the cooling rate was not important and the data are shown by crosses too.

In Fig. 5 we show how the difference between ”slow” and ”fast” coolings looks like. As a result of the ”fast” cooling, $`\nu _2`$ widens uniformly. A similar broadening effect can be seen in IR reflectivity spectra too, as it is shown in Fig. 6. In the latter case, the integrated intensity of the phonon line did not depend of the cooling rate.

An increase in the linewidth with decreasing temperature looks quite unusual in itself. It can be seen also in $`\delta (\nu _2,𝒄,4)`$ and $`\delta (\nu _2^h,𝒄,0)`$ (Fig. 3). The disorder in ethylene groups produced by fast cooling occurs approximately from 150 down to 50 K (Refs. Saito et al., 1999; Akutsu et al., 2000). It is also this temperature region that we found to influence our results for d. The phase separation occurs below 80 K (Ref. Taniguchi et al., 1999). So it would appear reasonable to relate the low-temperature broadening of spectral lines and the cooling-rate dependence of the linewidth with the phase separation rather than the ethylene-group disorder itself. However, the broadening can not be produced just as a result of differences between metallic and insulating phase in $`\omega (\nu _2)`$ and $`\omega (\nu _3)`$ because the broadening can be seen both in almost totally metallicTaniguchi et al. (1999) d and almost totally insulatingTaniguchi et al. (1999) d.

There is a possibility to explain the broadening by increased scattering of phonons at the domain boundaries. The amount of superconducting phase is very different in d, d, d and d, however, they all can have zero resistance below the temperature of the superconducting transition. So the bulk of the material probably consists of insulating domains embedded into the metallic matrix. It may be guessed that the characteristic size of insulating domains is the same for any sort of crystal. When the temperature decreases, the insulator–metal boundaries become more pronounced and can scatter phonons more effectively. Slow cooling increases the domain size in d, d, and probably in d, but, for unknown reason, not in d. An upper limit for an insulating domain size $`d`$ can be estimated as $`dc\tau c/\delta `$, where $`c`$ is the sound velocity, $`\tau `$ is the phonon lifetime, $`\delta `$ is the phonon linewidth. It gives several nanometres which is quite consistent with the model proposed by Yoneyama et al.Yoneyama et al. .

Another parameter that depends on the cooling rate is EMV dimer–dimer splitting of $`\nu _3`$ mode, $`\omega (\nu _3(A_g,B_{1g}))\omega (\nu _3(B_{2g},B_{3g}))`$. In Fig. 7, we show its temperature dependence for d and d. Above 50 K the splitting decreases significantly (by 25% per 200 K) with increasing temperature, and there is no considerable difference between mostly metallic d and mostly insulating d. For d below 50 K the splitting remains constant or maybe decreases a little with decreasing temperature. For d the splitting evidently decreases below 50 K, the linewidth $`\delta (\nu _3(B_{2g},B_{3g}))`$ substantially decreasing too (see the inset). (For d, d, d the values obtained for this linewidth were more scattered and no definite change could be detected.)

According to Eldridge et al.Eldridge et al. (1991), for d the behaviour of the intradimer EMV coupling is quite different. It continuously increases with increasing temperature but mainly below 100 K. For $`\kappa `$-(BEDT-TTF)2Cu\[N(CN)2\]Cl the temperature behaviour of the intradimer EMV coupling is different again, the splitting decreasing below 50 K and increasing above 100 K with increasing temperature.Kornelsen et al. (1992)

For the temperature behaviour of the interdimer EMV coupling we can consider two important factors. The first one is the temperature change of lattice parametersKund et al. (1993); Toyota et al. (1993) which can influence interdimer interaction more than intradimer interaction. However, calculations (see Ref. Nogami et al., 1994, for example) show that (i) the intradimer transfer integrals are influenced not less that interdimer ones and (ii) about 1 % change of the lattice parameters really taking place between 100 and 300 K leads to less than 10 % change in the transfer integrals. Probably, another factor, the temperature variation of the antiferromagnetic correlations, can be important. The charge transfer and EMV coupling act predominantly between dimers with antiparallel spins. Below $``$300 K these correlations increase gradually with the decrease of temperature.Nakazawa and Kanoda (1996) Only short-range correlations are important which can result in the absence of substantial difference between metallic d and dielectric d.

The influence of the antiferromagnetic correlations on the EMV coupling can be roughly illustrated in the frame of Rice’s dimer model.Rice (1979) If the spins are antiferromagnetically ordered then the dimer–dimer charge-transfer transition results in the singlet state with the effective dimer Coulomb energy $`U_{eff}^{}=2t_{ra}+U/2\sqrt{U^2/4+4t_{ra}^2}`$ (Ref. Kino and Fukushima, 1995), where $`U`$ is the intramolecular Coulomb energy and $`t_{ra}`$ is the intradimer transfer integral. If the spins are completely disordered then, in the half of all cases, after the dimer–dimer charge-tranfer transition there occurs the triplet state with the effective dimer Coulomb energy $`U_{eff}^{}=2t_{ra}`$. The difference $`U_{eff}^{}U_{eff}^{}=\sqrt{U^2/4+4t_{ra}^2}U/2`$0.15 eV (taking $`U`$1 eV, $`t_{ra}`$0.2 eV). In comparison with $`U_{eff}`$0.6 eV, it is a considerable value but the estimate is very rough because the value for $`U`$ is not accurately knownTajima et al. (1990); Parker et al. (1989); McKenzie (1998). In addition, $`U`$ is affected strongly by the screening effect. We can expect that spin ordering leads to a decreased screening, thus increasing $`U`$ and enhancing the dependence of $`U_{eff}`$ upon spin–spin correlations.

However, there exists an opposite factor, namely, in the antiferromagnetic state as a result of the charge transfer an electron obtains an additional exchange energy, approximately estimated as $`32t_{er}^2/U_{eff}`$0.1 eV (interdimer transfer integral $`t_{er}`$0.1 eV). (As to the difference in the intermolecular Coulomb interaction inside a dimer between the singlet state and the triplet state, this difference is very small, less than 0.01 eV (Ref. Fortunelli and Painelli, 1997)).

The above-estimated values have opposite signs, and we cannot assess their sum even roughly.However, in any case the antiferromagnetic ordering can essentially influence $`U_{eff}`$ and, therefore, the EMV coupling.

Below 50 K the two-dimensional antiferromagnetic short-range spin–spin correlations are already almost as large as possible, both in insulating and metallic phases, increasing no longer. However, in the antiferromagnetic phase screening can continue to decrease with decreasing temperature that resuls to an increase of the intramolecular Coulomb energy $`U`$ and therefore to a small increase of $`U_{eff}`$ and to a small decrease of the EMV coupling. In such a case the decrease of $`\delta (\nu _3(B_{2g},B_{3g}))`$ for d can be explained as the result of decreasing amount of the metallic phase in the bulk of the crystal.

For d and d the dimer–dimer EMV splitting depends on the cooling rate. Fig. 8 demonstrates this effect for d. Below 80 K after ”slow” cooling the splitting is approximately constant (open diamonds on Fig. 8), after ”fast” cooling (solid diamonds) it decreases with decreasing temperature. At 5 K we estimate the splitting for d as 66$`\pm `$1 cm-1 after ”slow” cooling and 61$`\pm `$2 cm-1 after ”fast” cooling. For comparison, we also present in Fig. 8 the data for d (crosses). After ”fast” cooling the behaviour of d looks similar to d.

Concerning the intensities of Raman signal, for all the samples under the 514-nm laser irradiation, the ratio $`I(\nu _2,𝒃)/I(\nu _3,𝒃)`$ is temperature-independent, but the ratio $`I(\nu _2,𝒄)/I(\nu _3,𝒄)`$ increases linearly with decreasing temperature. To a first approximation the increase in $`I(\nu _2,𝒄)/I(\nu _3,𝒄)`$ occurs purely at the expense of $`I(\nu _2,𝒄)`$ increasing linearly. Under 633-nm laser excitation $`I(\nu _2,𝒄)/I(\nu _3,𝒄)`$ is temperature-independent in all compounds. For d, $`I(\nu _2,𝒄)/I(\nu _3,𝒄)`$ also depends of the cooling rate. Such temperature dependences and the cooling rate dependence of $`I(\nu _2,𝒄)/I(\nu _3,𝒄)`$ are connected with the fact that $`\nu _2`$ mode is in resonance with $`𝒄`$-polarised 514-nm laser irradiation but $`\nu _3`$ is not. At low temperatures resonance conditions improve and $`I(\nu _2,𝒄)`$ increases, $`I(\nu _3,𝒄)`$ remaining constant. For d, fast cooling increases disorder and worsens the resonance conditions, acting similar to the heating.

Fig. 9 shows the correlations between the parameters influenced by cooling rate for d. The temperature was 5 K. We put here also the data obtained in a period when we were looking for a good ”slow” cooling procedure and were trying different methods (’+’ symbols). In Fig. 9 ”slow” and ”fast” data occupy different areas, especially in $`\delta (\nu _2)`$ direction. Except that, however, there are no evident correlations between $`\delta (\nu _2)`$ and the dimer–dimer splitting of $`\nu _3`$. The same can be said about the other possible pairs (not shown): $`\delta (\nu _2),I(\nu _2,𝒄)/I(\nu _3,𝒄)`$; and $`I(\nu _2,𝒄)/I(\nu _3,𝒄),\nu _3`$ dimer–dimer splitting.

d is very sensitive to a cooling procedure, more than d. We found that when we cooled the sample with approximately constant rate 1 K/min from 150 down to 50 K without any interruptions, we obtained the biggest difference with the ”fast” cooling procedure. This temperature region can not be narrower. We also tried annealing for 6 hours at 70 K or 30 minutes annealing after every 10 K from 150 down to 50 K but the results were, surprisingly, worse (i. e., the difference with the ”fast” cooling was smaller). We cannot explain this. Cooling rate 0.5 K/min makes no difference from 1 K/min. Contrary, near the ”fast” cooling limit the cooling rate looks quite important, because stable results near the ”fast” cooling limit could be obtained only if the transfer tube is well precooled.

According to Ref. Kawamoto et al., 1997 the amount of dielectric/metallic phase for d is sensitive to the cooling rate mostly near 60–90 K, at higher temperatures cooling rate being not so important. From the fact that for our data the cooling rate is important in a wider range of temperature (50–150 K) we can suggest that probably any cooling rate dependence found by us results directly from different amount of disorder, not from change of an amount of metallic/antiferromagnic phase produced by the phase separation.

Specifically, the decrease of dimer–dimer EMV coupling below 80 K for d, d (Fig. 8) can be either an intrinsic property of the insulating phase or a consequence of disorder induced by deuteration and/or fast cooling. We think that the latter looks more reasonable, mostly because for d this decrease depends on the cooling rate.

The absence of correlations between different parameters shows that these parameters are not directly connected with each other suggesting, again, some kind of disorder.

However the strange thing about this disorder is that the disorder increases with decreasing temperature down from 50 K when the ethylene groups are already completely frozen. Probably for d and d fast cooling results in rather ”bad” antiferromagnet with very small domains or some other kind of spin disorder. Such unknown disorder can give another explanation (except the scattering on the domain boundaries suggested above) for the observed broadening of $`\nu _2`$ and $`\nu _3`$ with decreasing temperature.

## IV Conclusions

1. Below 20–40 K the width of $`\nu _2`$ and $`\nu _3`$ Raman lines can increase with decreasing temperature.

2. Below 50 K, in the antiferromagnetic d, dimer–dimer EMV splitting of the mode $`\nu _3`$ decreases with decreasing temperature.

3. A cooling rate dependence has been observed in d and d crystals for the linewidths of phonon modes both in Raman and IR spectra, and $`\nu _3`$ dimer–dimer EMV splitting in Raman spectra. The difference between slow and fast cooling can be seen below 20–50 K and increases with decreasing temperature. For d the influence of the cooling rate is essential from $``$150 down to $``$50 K. We explain the cooling rate dependences as a result of increasing disorder upon fast cooling.