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VOLUME 121, NUMBER 13
1 OCTOBER 2004
Complex autocorrelation function and energy spectrum by classical trajectory calculations
˘ˇ´ ´ Petra R. Zdanskaa)
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo 2, 166 10 Prague 6, Czech Republic
Department of Chemistry and Minerva Center of Nonlinear Physics in Complex Systems, Technion—Israel Institute of Technology, Haifa 32000, Israel
Received 14 April 2004; accepted 8 July 2004 A quasiclassical method which enables evaluation of complex autocorrelation function from classical trajectory calculations is proposed. The method is applied for two highly excited nonlinearly coupled harmonic oscillators in regimes prevailed either by regular or chaotic classical motions. A good agreement of classical and quantum autocorrelation functions is found within short Ehrnfest time limit. Fourier transforms of the autocorrelation functions provide moderate resolved energy spectra, where classical and quantum results nearly coincide. The actual energy levels are obtained from approximate short-time autocorrelation functions with the help of ﬁlter diagonalization. This study is a follow up to our previous work P. Zdanska and N. Moiseyev, J. Chem. Phys. 115, 10608 2001 , where the complex autocorrelation has been obtained up to overall phase factors of recurrences. © 2004 American Institute of Physics. DOI: 10.1063/1.1787489
Our present study is motivated by a quest for a method suitable for calculation of rovibronic spectra of nearly classical polyatomic systems, such as chromophores bound in van der Waals clusters,1–5 van der Waals matrices,6,7 etc. Calculation of rovibronic spectra of polyatomic systems represents a hardly tractable problem. Fully quantum treatment is possible for systems up to four to nine degrees of freedom,8,9 although for special cases systems up to 24 degrees of freedom have been calculated.10,11 Another possibility is mixed quantum-classical approach where a small important part of a system is simulated in quantum way, while the inﬂuence of the rest of the system is approximated by classical dynamics.12,13 The third type of approach uses a full semiclassical treatment.14 –17 Our present concern is a quasiclassical approach known as Wigner phase-space WPS method.18,19 All degrees of freedom are treated on the same footing, i.e., by classical mechanics, and quantum mechanics comes into the calculation only through the initial choice of positions and momenta of classical trajectories. All quantities are calculated without a speciﬁc evaluation of the semiclassical phase, which makes the WPS method promising for larger systems than those allowed by quantum and other semiclassical approaches. The other motivation of our study is a theoretical puzzle posed by the WPS approach. The WPS method is capable of very accurate approximations to cross sections19 or meanﬁeld potentials,20 namely, quantities which are dependent on quantum time-dependent wave function—not merely on its absolute value, but the phase, too. Therefore one asks, whether complex quantum amplitudes, such as the autocora
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relation function, can be obtained from WPS propagations, and if yes, then how? One possibility is to map timedependent phase-space density onto a wave function and thus to calculate the autocorrelation function in Hilbert space.21 Yet the backward mapping of classical evolved phase-space density includes a conceptual problem, as long as classical and quantum evolutions result in general case in very different phase-space densities.19 Thus the introduced error may be hard to estimate in unknown systems. Counter to one’s intuitive notions, the expectation values calculated from the classical evolved density are rigorous approximations to quantum expectation values,22 due to, loosely speaking, vanishing of the oscillatory part of the quantum density upon the integration. Therefore we suggest to utilize expectation values of the product Hamiltonian—evolution operator rather then the backward mapping of the classical evolved phase-space density, in order to calculate the phase of the autocorrelation function. Our paper is organized as follows: In Sec. II we summarize the theory for the WPS approach needed for derivations of new formulas. In Sec. III we summarize the results of our previous study:23 We show that the phase of autocorrelation function can be deﬁned using expectation values of the product operator of Hamiltonian and evolution operator. This deﬁnition results in the phase integration which has to go through regions in time domain of zero amplitude, therefore the phase of individual recurrences is obtained only up to the relative phases between recurrences.23 In Sec. IV we propose a solution to overcome this difﬁculty. We deﬁne an auxiliary cross correlation function with a frozen wave packet which propagates on a classical periodic orbit. The cross-correlation function does not vanish which allows for integration of the phase, and coincides with
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V and VI.jsp . C 2 . of the autocorrelation function be deﬁned as C t C t ei C t The WPS method is a quasiclassical approach to quantum dynamical problems. ii Phase-space points.p j . which are approximated by Eqs. Phase-space points are preferentially distributed in the region of P such that the weight.pi t . 3 ˆ where A corresponds with A through the Wigner-Weyl transˆ given by form of the operator A A q. P is represented as the ensemble of phase-space points. 1 October 2004 ˘ˇ´ ´ P. The potential operator is expanded in Taylor series such that. and the point is selected if w i N. 7 ˆ is obtained for A being the initial density operator.p 1 2 F . 6 Following this. ˆ A (t). are evolved in time by classical propagation.pi (t) .org/jcp/copyright. While in the regular case Sec. the weight is compared with the randomly generated number. the survival probability is approximated within the WPS method by C t 2 i P qi t . It is convenient to calculate separately the potential and kinetic contributions. consisting of three steps: i The initial phase-space density P is obtained as a Wigner transform of the initial wave function . the phase is calculated using expectation values. 12 ˆ Ae ˆ i/ H t 2 are approximated by the phase space integrals. AV d qe i/ V q p• q q• p q q/2 * q q/2 13 ˆ In practice. A is calculated using Eq.t .25 in Secs. in the chaotic regime one has to deﬁne multiple periodic orbits to follow individual recurrences Sec. qi . see http://jcp. w j P(q j . We demonstrate our techniques for the model PullenEdmonds Hamiltonian of two nonlinearly coupled harmonic oscillators24. is ascribed to every randomly generated point q j . the survival probability C(t) 2 deﬁned as the absolute value squared of the autocorrelation function C(t). iii The quantum expectation values. we calculate the Wignerˆ Weyl transform AH of the operator A H using Eqs. 1 where ˆ H ˆ R H . 3 and 6 . is obtained using the known WPS approximation given by Eq. C (t). Redistribution subject to AIP license or copyright.aip. 9 By differentiating the identity C(t)/C * (t) exp 2i C(t) we obtain the expression for the time derivative of the phase given by C 1 d qe i/ q/2 p• q t q/2 . Downloaded 14 Jan 2005 to 132.. C t e ˆ iH t/ . PHASE OF AUTOCORRELATION FUNCTION Calculation of the complex autocorrelation function is considered fully within the realm of the WPS method.1. In Sec. A (t) is evaluated by Monte Carlo integration over classical trajectories. VI . VIII we present our conclusions. VII we demonstrate the application of Fourier transform and ﬁlter-diagonalization26 –29 methods to calculate the energy spectra from classical approximations to autocorrelation functions.p P q. where AV is the ˆ ˆˆ Wigner-Weyl transform of A V P V and AT is the Wignerˆ T . ˆ P Following the WPS approach. R. 11 ˆ and P is the density operator deﬁned as ˆ P . Vol.6176 J. 8 III. 3 and 6 . The nominator is deﬁned as the ˆ ˆ ˆ expectation value P H (t) of the product operator A H ˆ H. Phys. namely. ˆ A t dq dpA q. 121. qi (t). 4 5 Equation 11 allows us to calculate the phase using the timedependent expectation values.p d qe i/ d pe i/ p• q q p ˆ q/2 A q ˆ p/2 A p q/2 p/2 . The survival probability. V a single periodic orbit is sufﬁcient to follow the periodic motion. yet the calculations differ in the effort required. WIGNER PHASE-SPACE APPROACH ˆ A t i A qi t . qi . Let the phase. AH AV AT . 4 as ˆ ˆ Weyl transform of A T P V ˆ long as A V includes the potential operator commuting with coordinate representation. and thus the complete autocorrelation function can be calculated: phase and amplitude. P q. represent the time-dependent classical phasespace density P(t). 13. therefore in Sec.p j ). The main importance of obtaining the autocorrelation function is that it can be used to obtain the energy spectrum. The obtained trajectories.pi t .29. This designed coincidence enables us to obtain the relative phase between recurrences. q/2 . Our calculations give an evidence that the presented method works in regular and chaotic regimes alike. which in turn are accessible by the WPS approach using Eqs. 8 .pi . 4 and 5 . No. II. 10 q * q where F is the system dimension.p. N max P . deﬁned as ˆ A t e i/ ˆ Ht ˆ ˆ ˆ e iH t/ P H e ˆ iH t/ C 2 . .pi . Moiseyev the required autocorrelation function at periodic time intervals.68. Chem. Zdanska and N.
when only the ﬁrst term of the serie for RAH . C iH 2n d 0 4 V 1 2n 1 2n 1 P 1 d 2n 1 T 1 2n 1 P 1 t . is included.pi t i P qi t .. Again. 18 IAH 1 2n 1 ! By comparison of Eqs. using of Eq. 15 and we obtain the series for AV given by. Chem.pi t iA 2 n! n qn . 11 –using Eqs. C 1 i RAH t qi t . 2 n n! dqn qn d n V 14 correlation function. 10 . No. represents the inherent error of the WPS approximation. 10 such that. the phase is known for individual recurrences only up to a constant phase factor.org/jcp/copyright. 21 The phase of the autocorrelation function is calculated by numerical integration using the phase derivative over time. 19 is included. Redistribution subject to AIP license or copyright. 21 and 25 one can see that Eq. 20 The phase of the autocorrelation function is calculated using Eq. 6 . all consistent with the WPS assumption Eq. which coincides with the autocorrelation function at a single point within each recurrence. 25 dq2n p2n dp2n q2n ˆ We obtain the WPS approximation for H by substitutions into Eq.23 The solution of this difﬁculty is addressed in Sec. Downloaded 14 Jan 2005 to 132.68. The derivation of the phase derivative.29. 22 using the quadratic approximation. On the other hand. 18 . A. 8 . 22 . We use the following property of Fourier transform. 8 is used for the denominator. Vol. 2 n RAH n 0 4 d 2n V dq 2n 2n 1 2n ! P d 2n T dp 2n 2n P p 2n 2 n q 2n . IV. 22 and 23 one can see that Eq. 5 . Eq. Eq. 23 is obtained from Eq. 13 . 25 results in values of C / t which are incorrect for harmonic oscillator.pi t P qi t .pi t i . H p2 /2 q2 /2. therefore the WPS approximation to autocorrelation amplitude is exact in the case of harmonic oscillator. An alternative to the WPS approximation. 17 . In order to clarify the role of the quadratic term in calculation of the phase derivative. 21 . 1 exp F/4 q q0 2 2 i q"p0 .pi t P qi t . where we deﬁne and evaluate a cross- The proof of Eq. Similar discussion is possible for the time derivative of the autocorrelation phase. is applicable also in the case of autocorrelation amplitude. 13. is the expression given by. Eq..pi t P qi t . see http://jcp. Using Eq. the phase derivative between the recurrences cannot be calculated for the reason of numerical inaccuracy. 23. AT i n 0 n d nT dp n n P Another way to obtain the time derivative of the autocorrelation amplitude. we obtain ln C t 1 i IAH d nV dq n n P n 2 n! n p .jsp . As a consequence. e. 1 we obtain the corresponding Wigner distribution given by. C 2 . ˆ H i AH qi t .1. 22 ˆ The Wigner-Weyl transform of A T is obtained in the same manner using the momentum representation.pi t i . 21 . 25 can be found in Ref.pi t P qi t . by comparison of Eqs. 19 . is by differentiating Eq. One can see that Eq. 16 qi t . The existence of different formulas for same quantities. Let us demonstrate this point for the case of autocorrelation amplitude. d qe i/ p• q q P q/2 * q q/2 qn n i n pn . while Eq. when only the ﬁrst term of the series for IAH in Eq. Therefore in such cases. 19 qi t .pi t i P qi t . and 19 we obtain the WPS approximation of the nominator. 21 .pi t i . 25 is given by the linear approximation to Eq.g. ln C t where A dV P dq p dT P . 23 is obtained from Eq. Fig.pi t . Eq.J. 121. doing this and using Hamilton’s equations of motion we obtain the expression. 26 where the harmonic Hamiltonian is given by. AV i n 0 n In this section we discuss inconsistent expressions for autocorrelation function. 1 October 2004 Energy spectrum by classical trajectories 6177 V q q/2 n 0 . 23 ˆ The Wigner-Weyl transform AH of A H is a complex function given by the series for its real and imaginary parts. which are derived using different algebraical approaches. Eq. In cases where the autocorrelation function consists of well separated recurrences see. 25 is obtained from Eq. 6 . dp q 24 1 2 qi t . let us consider the case of a coherent Gaussian wave packet given by. 2 . Phys.aip. Inconsistency within WPS approach: The harmonic approximation This result is substituted to Eq.
. periods the values of C(t NT) are equal to X(t NT). is given by C t H F 4 q0 p0 .p i (t) E 0 E. 30 and is given by C We deﬁne an approximate classical periodic contour orbit ... 1 October 2004 2 2 ˘ˇ´ ´ P.68. In this way we avoid numerical difﬁculties in extracting time-dependent phase derivatives between recurrences where C(t) 0. it is reasonable to deﬁne (t) as the frozen wave i q• p0 pc 0 p0 • qc 0 qc t 38 Downloaded 14 Jan 2005 to 132.pi (T) . 2T.jsp .1. 4 31 t P qi T . 33 where X(t) is deﬁned as X t t e . Let us consider a quasiperiodic motion with the approximate period T. Vol.pc (t) .pc (t) .org/jcp/copyright.29. Further we conﬁne to trajectories falling within a small energy interval E 0 E H q i (t). R. IV. after T. qc0 (t)..pc0 (t) satisfy the condition of api proximately following the classical phase-space packet. To assure this condition. C i pi i i t F 2 q0 p0 . It is evident from this discussion that the second-order term is responsible for one half of the zero-point energy shift in the case of coherent harmonic motion. 25 . (t) is given by t 1 exp F/4 q q0 qc 0 2 pc t i qc t 2 The idea is to deﬁne (t) in such a way that there are no revivals in X(t) and therefore unlike C(t). here we suggest the following procedure: i positions and momenta of evolving trajectories are weighted by P qi (T). this is especially reasonable in cases when the wave function bifurcates due to time evolution. Phys. Classical periodic contour F 2 1 2 p p0 2 q q0 2 .and second-order contributions leads to the correct result. (NT) . C/ 28 t.pc (0) qc (T). C iH H 2 2 t qi t . as de- The contribution of the zero-order term to ﬁned by Eq.6178 J. 2 32 which is in aqreement with the quantum-mechanical deﬁnition given by Eqs. B.1. 37 N 0. see http://jcp. such that qc (0). 18 .pc (T) . 34 that represents a frozen wave packet which keeps the shape of the initial wave function while its position is changed according to the classical periodic contour.aip. however. qc (t). ii The second condition is that the contour must form a closed loop.. notice that in this case the left vector (t) depends on t parametrically. Chem.pi T t P qi T .. 10 and 11 . It is thus expected that an error of about one half of the zero-point energy is caused by omitting the quadratic term in series Eq. No. 18 . RAH can be written as the sum of zero-order and second-order terms. The idea is to deﬁne the new function (t) such that (t NT) and therefore. Except for approximately following the motion of the classical phase-space density. to give a large preference to those contributing to a given autocorrelation recurrence. 13. 27 The Hamiltonian H and the Wigner distribution P are substituted into Eq. 35 . the periodic contour can be arbitrary.pi t . Moiseyev P 1 exp F q q0 p p0 ..pi t P qi t . 36 dt exp i 0 In this section we show how over-all phase factors of autocorrelation recurrences can be obtained. ˆ iH t/ where n acquires small integer values pc (t) is obtained similarly.pi T i P qi T . Then we may assume that a recurrence in autocorrelation function occurs for time t T. Redistribution subject to AIP license or copyright. X(t) represents a cross-correlation function. CROSS-CORRELATION FUNCTION E H q i (t). A. The sum of the zero. RAH PH PH (2) .. qc (t).p i (t) E 0 E and where i 1 for E 0 0 otherwise. Frozen wave packet We deﬁne a wave function t e i/ pc t ˆ pc 0 q (t) given by qc t ˆ qc 0 p e i/ . C NT X NT . The ﬁrst estimate of the classical contour according to this procedure is given by qc0 t pc0 t i qi t H 2 F .pi T i i . which is accomplished by using the back-andforth Fourier transform: qc t exp n T i 2 nt T 2 nt T qc0 t .pi t i P qi t . 121. etc. in contrast to the most common deﬁnition of crosscorrelation function. X(t) does not drop to zero between the recurrences. Zdanska and N. 2 29 The contribution of the second term is calculated using the equation. where H (2) is given by H 2 packet moving according to the classical periodic contour. The wave packet (t) acquires the important property.pi T i P qi T .
X 2 . The initial wave packet 0. V. Vol. deforms and starts to develop nodes. which is set far in classical mixed regular-chaotic regime.pi t such that X t where P q.p. q/2.. qi t . as shown in Ref. of the cross-correlation function is deX t X t ei .pi t . . The corresponding energy expectation value is 21 a. ˆ The WPS approximations for the integrals R H ˆ and R p .pi t pi t . The system is illustrated in Fig. where A ˆ Aa is given by the Wigner-Weyl transform of A a ˆ a . 43 and 47 . 2T. the WPS approximation given by Eq.29. 1 2 48 ˆ where the notation a ˆ a ˆ ˆ ˆ H . We conﬁne our study to a short-time propagation.u.aip.pi t qi t . 33 .u. 39 ˆ R q ˆ R p qi t . As discussed before.u.. AH . This is approximately the Ehrnfest time for the studied system.t 41 * q The phase. 40 . P p.. The wave packet. from the calculated classical cross-correlation function. 45 The Wigner-Weyl transforms. These are listed below: 2 RAH P H n 1 2n 4 P 1 2n ! d 2n T dp2n 2n d 2n V dq2n RAq RAp P q. the complex cross-correlation function X(t) is calculated using the WPS approach. C. Redistribution subject to AIP license or copyright.pi t qi t . Aq .t . which serves as the benchmark for our study. allows us to calculate the exact autocorrelation function Eq. Downloaded 14 Jan 2005 to 132. p0 0. ﬁned as X t X. we derive the expression for the time derivative of X given by X To summarize. The initial position of in the phase space is q0 4 a. Chem. a ˆ iH t/ The Pullen-Edmonds Hamiltonian is given by pc t . this is not true for the autocorrelation function C(t) which can be evaluated from classical trajectory calculations for individual recurrences only up to the overall phase factors. 23. for one classical period. see http://jcp.jsp . For the chosen. The autocorrelation function C(t) includes three well distinguished recurrences. 26 .t . ILLUSTRATION FOR REGULAR SYSTEM 1 t ˆ R H ˙ ˆ q• R p ˙ ˆ pc •R q pc 0 ˆ .p . 43 . 42 By differentiating the identity X(t)/X * (t) exp 2i X(t) . ˆ P t t t . 1 October 2004 Energy spectrum by classical trajectories 6179 for the case of initial Gaussian wave packet deﬁned by Eq. 46 It represents two nonlinearly coupled harmonic oscillators. 26 . 1. 40 q q/2. is evaluated using Eq. 43 V q 2 /2 q 2 /2 1 2 T 44 p 2 /2 p 2 /2. P p2n q2n . Eq. as shown in Fig.pi t qi t . 6 is correct. X / t. where all trajectories acquire the same Maslov indices at a time. approximately. The absolute value X is obtained using Eq. 6 . for three classical periods. stands for . 10 a. as shown in Ref. 23. . 121. which is given by Eqs. Once this condition is satisﬁed..J.pi t . 7 for this time period. but stays localized.. we obtain the correct phase of the autocorrelation function at T.23 Using the equivalence Eq.pi t . 47 Calculation of complex cross-correlation function X(t) by the WPS approach is similar as in the case of the autocorrelation function. ˆ a i Aa iP qi t . Phys. the system For energies beyond a given energy limit becomes mixed regular and chaotic.957 a..0 .68. are given by ˆ R H i RAH iP iP ˆ . which is evolved. 40 . are complex functions whose only real parts are used to calculate the cross-correlation phase Eq. the energy limit is given by the Gaussian function. as long as it does not include revivals nor drops to zero. is evaluated using P ˆ Eq.pi t iP iP qi t .u. 2.05. The absolute value square X 2 is obtained as the expectation value of the density operator.R q . P a . 2. i P qi t .t d qe i/ p• q 2 i P qi t . Thus the missing overall phases of autocorrelation recurrences are determined and the classical complex autocorrelation function is obtained. and Ap . while the phase X is obtained by numerical integration of its time derivative.1. Absolute value and phase of cross-correlation function qi t .org/jcp/copyright. 1 2 q 2q 2. ˆ ˆ ˆ e iH t/ P a e X 2 ˆ The WPS approximation to a is obtained as follows: the ˆ ˆ nominator. The prevailed motion for this wave packet is regular.q. The contour plot of potential illustrates its nonlinearity which displays itself by deviation from circular curvature. The quantum-mechanical propagation. No. The crosscorrelation function X(t) can be evaluated numerically in the time interval from t 0 to t NT. and the denominator. 13.
Moiseyev FIG. The cross-correlation function X(t) is deﬁned by Eqs. These points are emphasized in both Figs. For an illustration. Their quantum deﬁnition is given by Eq. III A. 50 where A H H H (2) .pi t . 2–3. 35 – 36 .2T. shows an excellent agreement. Chem. which are chosen by means of preferential sampling of the initial phase-space density. The absolute value and the real part are denoted by black and gray lines.. 13. the p p0 pc 0 pc t . 3. t 2 2. 3 and 5. P 1 q q0 qc 0 2 exp F qc t 2 The deﬁnition of the cross-correlation function is based on a notion of classical periodic contour orbit . cross-correlation function is a means to obtain the phase of the autocorrelation function at time points t NT. Cross-correlation function The absolute value of cross-correlation function is evaluated using Eq.2T. B.u. The Pullen-Edmonds potential is drawn by dashed contours. where the cross-correlation function coincides with the autocorrelation function. A. FIG. Cross-correlation function by quantum propagation for the time interval 0 t 11 a. X (t) does not climb down to zero.u. 27 . is obtained by substitution of Eq. The values at t T. qc (t).jsp . 1. 43 . Autocorrelation function calculated by exact quantum propagation for the time interval 0 t 15. is the sum of the classical Hamiltonian H and the quadratic term H (2) . Let us discuss in detail the classical approximation of the quantity R H in the light of the results obtained in Sec. The classical periodic contour is calculated using Eqs. respectively.29. with the period T.u. Fig. No. P . Redistribution subject to AIP license or copyright. Figs. see http://jcp. The time derivative of X is calculated from the ˆ ˆ ˆ integrals R H . ˆ 4 a and 4 b .3 a.3T are emphasized by dots. which is addressed below. t 3 3. nor creates recurrences. while their WPS approximations are given by Eqs. The phase of the cross-correlation function X is calculated using numerical integration of the time derivative.aip. 121.5 a. and t 4 4. 47 . The Wigner-Weyl transform of . 40 . 46 and 47 . R. Zdanska and N.65 a. Phys.3T .. 5.u. leads to the expression R H iA H FIG. 35 and 36 .pi t ]P qi t . Vol. Classical trajectory calculation of cross-correlation function The classical trajectory simulation is performed for an ensemble of trajectories. P.pi t i P qi t .pi (t) . 1 October 2004 ˘ˇ´ ´ P. One-period wave packet evolution. which approximately represents the classical periodic motion of the phase-space density. X / t. 44 . qc (t) is illustrated in Fig. 41 . 1.1. The quantum and ˆ ˆ classical results for R q and R p are displayed in Figs.5 a. P is deﬁned by Eq.6180 J. we evaluate the crosscorrelation function using quantum mechanics. Downloaded 14 Jan 2005 to 132. are emphasized. Eq. 3. respectively. In the classical trajectory method. The values for t T. 48 to Eqs. which serves in the deﬁnition of the cross-correlation function. 34 – 38 . The wave packet is shown at times t 1 0. 38 to Eq. the WPS approximations for R q ˆ and R p given by lines are in an excellent agreement with the quantum results given by points . The evolved wave packet intersects the closed contour Eqs. Unlike the autocorrelation function. Clearly.u. qi (t). R q .pc (t) . This property is essential for its accessibility by the classical trajectory method. The absolute value and the real part are denoted by black and gray lines.68.. where the two functions coincide. The comparison of quantum and classical results for X 2 . The latter is given by. and R p .org/jcp/copyright. qi t . The substitution of Pullen-Edmonds Hamiltonian Eq. 49 The absolute value as obtained from classical trajectory calculation is shown as part of Fig. 2.
The points t NT.602 0. are emphasized. 4 c we show these two approximations lines compared with the quantum result points .jsp .29. dashed line—classical .45 a. As shown in Fig. 51 f As discussed in Sec.J. 44 calculated by ˆ circles—quantum.226 0.304 ˆ ˆ ˆ FIG. Convery large. The contribution of H (2) is relatively small due to high expectation value of energy compared to the zero-point energy.. in the case of harmonic oscillator. A H H. err-error of the classical values. 13.70% H class 0. R q . which appear in each classical period T. respectively. dashed line—one-term classical approximation. t T 4. deﬁned by Eq. or by a series. close to the quantum benchmark. The classical complex cross-correlation function is displayed in Fig.2T.543 0. Phase of the cross-correlation function at points t T. c R H circles— quantum.3T . quant –exact quantum values. III A. The absolute value and the real part are denoted by black and gray lines. and A H can be substituted either by Hamiltonian only.u. C. The points t NT. it is necessary to determine the phase of the autocorrelation function for at least one time-point per FIG. class is the phase as obtained by classical calculation in the quadratic approximation.68.1. H (2) .5 a. is evaluated from C / t by numerical integration and is known for individual recurrences up to overall phase factors. 0. 8 . solid line—classical and R p 2 ˆ triangles—quantum. a R q 1 ˆ solid line—classical and R q 2 triangles—quantum. class includes the error sequently. Cross-correlation function obtained by classical trajectory calculations for the time interval 0 t 11 a. This value is close to the half of zero-point energy. We can conclude that both approximations provide similar The absolute value of the autocorrelation function C 2 (t) is obtained using Eq.u. 6. Downloaded 14 Jan 2005 to 132. the WPS approximation for H is not unique.45% 0. FIG.2T. results.967 0. In Fig. R p . 5. the autocorrelation function includes three recurrences. are emphasized.440 0. Autocorrelation function obtained by classical trajectory calculations for the time interval 0 t 15. To adjust the overall phase factors. 121. solid line—twoterm classical approximation . We are able to evaluate the time derivative of the phase C . b R p 1 circles—quantum. see http://jcp. quantum and classical trajectory methods. quant is the phase as obtained by quantum calculation.428 0. err class quant /2 .885 quant class err 3. represented here by the sum.625 2T 9. A H H. dashed line— ˆ ˆ classical . The phase. 6. energy spectrum corresponding to the linear ap/(3T) proximation includes the error estimated by. The quantitative comparison of the quantum and classical cross-correlation functions is given in Table I.aip. which are used to obtain the phase of the autocorrelation function.255 3T 13. which are obtained from the phase of the cross-correlation function.u. Redistribution subject to AIP license or copyright. Phys. respectively.org/jcp/copyright. where the cross-correlation function coincides with the autocorrelation function in regular regime. as discussed in Sec. H and class is the phase as obtained by classical calculation in the linear approximation. III A. Classical trajectory calculation of autocorrelation function H 2 F 2 1 2 F f p p0 F 2 q q0 /2 pf q2 f 2 q2 f pf0 2 . and R H . 21 . where we list the phase of the cross-correlation functions at points t T. A H H H (2) .295 0. No.60% 8. The absolute value and the real part are denoted by black and gray lines. A H H H (2) . C . class. this result is in agreement with the role of the quadratic term. using classical trajectory calculations. Vol. It is clear that class is a H good approximation to quant . while the error of class is H 2 at t 3T. 4. M class –classical quadratic and linear approximations.3T . Chem. respectively. 5.428 0. 1 October 2004 Energy spectrum by classical trajectories 6181 TABLE I. given by Eq.
T 3 . 121.277 0. with periods T 1 . 23. VI. 13.aip.. we use the same type of Hamiltonian Eq. where the initial Gaussian wave packet is centered at nonzero momentum position.. 27 is propagated.. Within the time interval 0 t 15.164 0. here we choose q0 4 a.jsp .. 4 a. see http://jcp.57 14. Five cross-correlation functions are displayed...645 a. we could identify a quasiperiodic motion with a period T.. as shown in this section. This becomes evident after a close look at quantum autocorrelation function. These points are determined by the cross-correlation function for the time points t NT. It is clear that the classical calculations provide a good approximation to the chaotic autocorrelation function with the exception of the second recurrence. we deﬁne ﬁve periodic contours according to Eqs. Zdanska and N. Phase of the cross-correlation function at points t T 1 ..377 Downloaded 14 Jan 2005 to 132.3T are listed in Table I. At t 14 a.6182 J.. Quantum autocorrelation function for chaotic regime.427 0. the complex autocorrelation function obtained entirely from classical trajectory calculations is shown in Fig.u. The chaotic motion.u.141 0. In Table II we list the classical and quantum phase at time points t T 1 .1. therefore recurrences are multiplied and appear at irregular time spacing. from cross-correlation functions of their own periodic contours. .. Phys.31 quant class err 1.0508 0.u.32 9. Moiseyev FIG. class –classical quadratic approximation.. shorter than expected. 7.52% 5.68.org/jcp/copyright. The ﬁrst recurrence appears for t 5 a. 35 and 36 . When the corresponding phase-space packet Eq.5 a... TABLE II. Thus. the phase error FIG.592 0. but the recurrence time is by 1 a. where the cross-correlation functions coincide with the autocorrelation function in chaotic regime. 6.80 11. 1 October 2004 ˘ˇ´ ´ P. 8.. its large portion occupies chaotic sea.87% 68.u...2T.T 5 . where C (NT) X (NT). No. Redistribution subject to AIP license or copyright.29. three small recurrences are found. recurrence by another calculation. R.u. err–error of the classical values. In regular regime. Eq.u. quant –exact quantum values. Each recurrence in the autocorrelation function is created by a different quasiperiodic motion.u. is characterized by bifurcations of the phase-space density. ILLUSTRATION FOR CHAOTIC REGIME Application of the new method in chaotic regime is possible with a small modiﬁcation.16% 0.T 5 . causing a sequence of equally spaced recurrences. 8 a – 8 e .77 0. there is a large recurrence. therefore the phase of each recurrence is obtained using a different cross-correlation function.179 0.T 5 for individual quasiperiodic motions are emphasized. 48 .294 0. indicating a bifurcation to three different quasiperiodic motions. where the error of nearly 70% is obtained. 7. Fig.27 10. The corresponding ﬁve classical cross-correlation functions are displayed in Figs. 33 . 1. and p0 0. In place of a second recurrence at t 10 a. The total phase of recurrences is obtained for each recurrence separately.65% 4. Chem.u. err class quant /2 . Vol. For illustration. t T1 T2 T3 T4 T5 5.. The bifurcations of the time-evolved phase-space density must be reﬂected by different periodic contours for each recurrence. The particular phase values at points t T. the period of which corresponds to three approximate classical periods. Classical cross-correlation functions for chaotic regime. However.. It is assumed that this error is caused by the interference of trajectories with different Maslov indices the Ehrnfest criterium is not perfectly satisﬁed .. as can be shown with the ´ help of Poincare surface of section. Ref. Classical periods T 1 . on the other hand.11% 7.
The energy window width is given by the standard deviation 1. The classical autocorrelation function for chaotic regime is shown in Fig..u. does not take a great effect in the corresponding energy spectrum due to the relatively small amplitude of the second recurrence. 7 is remarkable. b chaotic regime. FIG.. 9.u. Redistribution subject to AIP license or copyright.8. 121. Phys. b chaotic regime. The classical approximation is in qualitative agreement with quantum spectra in both regular and chaotic cases. at points t T 1 .aip. 52 . 1 October 2004 Energy spectrum by classical trajectories 6183 FIG. k 1¯160. The absolute phases of individual autocorrelation recurrences are obtained from the corresponding cross-correlation functions.1. The evolution and overlap matrices are given by. VII. is the time of the propagation.u. U kk S kk t max 0 t max 0 dt dt e i Ek E k t/ C t t . 52 Limitation of our method to short-time propagation allows evaluation of moderate resolved energy spectra using Eq. 10.. The predominant role of the autocorrelation function in most calculations is that its Fourier transform gives energy spectra together with the corresponding Franck-Condon amplitudes I(E) as given by the equation.05 a. as shown below. E 23. Moderate resolved spectra as obtained by Fourier transform of the classical gray and quantum black autocorrelation functions for a small energy interval. a regular regime. The actual quantum energy levels and Franck-Condon overlaps are shown by vertical lines.5 a. The precision of the calcu- Downloaded 14 Jan 2005 to 132. which are shown in Figs.T 5 . which gives an optimal convergence of the ﬁlterdiagonalization method.jsp . we can see that the spectral peaks appear near the occupied energy levels. ENERGY SPECTRUM FROM CLASSICAL AUTOCORRELATION FUNCTION FIG. The agreement between the classical and quantum results Fig. 10 a and 10 b . see http://jcp. 13. The present implementation of the ﬁlter-diagonalization method is described below: i The Fourier transforms of the time-dependent wave packet.. a regular regime. has been calculated.67 a. which are selected to follow a bell distribution around the energy window center E 0 . III with no alteration for the chaotic regime.J. 11 a and 11 b . which are shown by vertical lines.68. for which the autocorrelation function 0. t max k 0 dte ˆ i H E k t/ 53 are used as basis functions to ﬁnd the eigenvalues of the ˆ ˆ evolution operator.5 a. is shown in Figs. 9. is a short-time interval. No. of energy grid points E k .u. 11. Classical autocorrelation function—chaotic regime. Moderate resolved spectra as obtained by Fourier transform of the classical gray and quantum black autocorrelation functions for the whole range of occupied energies. Calculation of the classical autocorrelation amplitude and time derivative of the autocorrelation phase is done according to Sec. The spectral interval 18. The actual energy levels can be obtained even from short-time propagations with the help of ﬁlterdiagonalization method. ii The basis functions k are deﬁned by energy grid points E k . I E R 0 dt exp i/ Et C t . Vol.26 –28 Here we apply the ﬁlterdiagonalization method to classical autocorrelation functions in regular and chaotic regimes in order to demonstrate the ability of the WPS approach to approximate the exact quantum energy levels. 54 dt dt e i Ek E k t/ C t t .. U ( ) e iH t/ . Chem. t max 15.29.u..5 a.org/jcp/copyright.
12. 19 a.002 TABLE III.4512 21.0007 0.003 0.0650 19.org/jcp/copyright.0006 0.018 0.u.0224 0. VIII.530 22. which signiﬁes the incomplete representation of Hamiltonian due to short-time propagation. E class E quant 18. see http://jcp. We suggest a way to overcome a problem of lost overall phases of separate recurrences.778 20. and proves to work in good quantitative agreement with quantum benchmarks.0001 0. Using the approximate complex autocorrelation function we attempt to calculate the energy spectrum of the system with the help of ﬁlter-diagonalization method. b chaotic regime.123 21. 13. The solution may hint toward separation of autocorrelation recur- Downloaded 14 Jan 2005 to 132.aip. respectively.020 0. The quantum and classical results are marked by black and gray color.924 19. It is thus characteristic that the standard error of the obtained energy levels is almost one order of magnitude larger in chaotic case compared to regular regime. namely.jsp .005 0.575 18.026 0. are listed in Table III and displayed in Fig.309 0.7858 20.025 0. Vol. 121.010 22.2 a.0252 0. 23 . Energy levels obtained by the ﬁlter-diagonalization method from the quantum and classical short-time autocorrelation functions in regular regime.8771 0.021 IV and displayed in Fig. The energy levels found in regular regime. Energy levels.027 0. E 23.0224 0.103 21.008 0.386 22.5291 23.29. We may thus conclude that the WPS approximation has been capable of prediction of energy levels in regular regime with the absolute error being 0.4288 21. The lost phase factors are obtained by calculation of a crosscorrelation function which serves as a link between t 0 and t T.’’ Italics added. E class –classical results. where T is the approximate classical period.u. Energy levels obtained by the ﬁlter-diagonalization method from the quantum and classical short-time autocorrelation functions in chaotic regime.0016 0.016 0. No.017 0.830 23.519 21.01–0. E class –classical results. 1 October 2004 ˘ˇ´ ´ P. without further modiﬁcation the classical Wigner method is not competitive with methods based on the VVG van VleckGutzwiller propagator expression.4992 23. E quant –quantum results.2182 23.5 a.1399 21. –absolute difference between quantum and classical values. The standard deviations are of orders 10 3 – 10 4 a.700 21.5 a.u.0303 lated energy levels is estimated as the standard deviation of few three to eight ﬁlter diagonalizations performed for different values of E 0 .015 0.68.020 0.023 0.0180 0. E 0 23.0007 0.025 0.03 a.1.u. a regular regime. We demonstrate that the Wigner phase-space approach is capable of prediction of energy levels of the given nonlinear system in regular regime with a very good precision. One of the main obstacles for practical application of the Wigner phase-space method. which is an error signiﬁcantly smaller than energy spacing between populated levels. which arise using the presented method Ref.01–0.248 20.0015 0.u. Chem.0025 0..5 a. in our experience the method is accurate only through intermediate times. E class E quant .361 19. Moiseyev TABLE IV.5 a.0020 0.036 0. however due to small energy spacing of occupied states the energy levels cannot be obtained.0064 0. is often larger than the energy spacing of the occupied levels in chaotic regime.212 20. One can see that the standard error of the ﬁlter-diagonalization method 0..0012 0. –absolute difference between quantum and classical values.307 0.406 22.037 0. E class E quant .024 0. We attempt the calculation of exact energy levels using the ﬁlter-diagonalization method in chaotic regime for the energy interval 18.708 21.328 19.u.807 20.0103 0. Phys.016 0.015 0.031 0.011 0.u.014 0. falling into interval 18.018 0.010 0.019 0.8121 22. and one of the main challenges of this approach can be expressed in words of Garashchuk and Tannor.u. E quant –quantum results.894 19.028 0.041 0.2118 23. 12 a . R.6184 J.0323 0. We formulate an approximation of complex autocorrelation function which is fully consistent with the Wigner phase-space approach.0021 0. The ﬁnite width of peeks is given by the standard error calculated for multiple ﬁlterdiagonalization calculations.. The obtained energies are listed in Table 18. We propose a quasiclassical method for calculation of complex autocorrelation functions within Ehrnfest time limit..999 22.0014 0.0299 0.0145 0. uses the rigorous quasiclassical expression for expectation values. CONCLUSIONS FIG.8181 20.032 0.8266 22. E 23.0007 0.022 0.027 0.0874 19. Zdanska and N. The error given by short-time propagation is also by one to two orders of magnitude smaller than the difference between the quantum and classical calculations given by the third column in Table III .029 0.557 18.027 0.020 0. as obtained by ﬁlter-diagonalization method bottom compared with Franck-Condon amplitudes top . The seven signiﬁcantly populated states are extracted both from quantum and classical autocorrelation functions.0008 0.1651 21.21 ‘‘Although we have been able to calculate the phase to the same accuracy as the amplitude.03 a. Redistribution subject to AIP license or copyright.u.0005 E quant 19. 12 b .. E class 19.9074 0.814 23.015 0. The method is tested for a model of two nonlinearly coupled harmonic oscillators for regular and chaotic regimes.
6 G. D. 290 1998 . and N. 117. Chem. 102. J. Chem. Chem.68. 173 1996 . Worth. Schmidt. B. R. Sci. J. Chem. Moiseyev. Phys. S. Hanz. Schmidt. Lett. Slavicek. and L. 7 M. A 56. Moiseyev. 1 October 2004 Energy spectrum by classical trajectories 10 6185 rences using the calculation of their Maslov index. Acad. 18 E. J. and D. 10761 2000 . 78. Phys. 8. U. J. and W.S. Chem. and D. 15 W. 52. Korsch. J. 29 E. 3578 1970 . Jungwirth. P. 276. J. 24 R. A 14. Sun. Math. 165. 19 E. J. Phys. Lett. Phys. 109. Vol. 5 2002 . 351 1996 . Phys. Jungwirth. Zdanska. H. Phys. R. Chem. A. Chem. see http://jcp. 4190 1998 . Korsch. Tannor. Prezhdo and V. C. Moiseyev. J. Phys. Phys. Garashchuk and D. Phys. and L. 287. J. Gerber. Chem. Phys. 3 P. 99. H. Cederbaum. and N. Phys. 177 1997 . Redistribution subject to AIP license or copyright. Kisil. 121. E. Washington. J. Phys. Hulme. Zdanska and N. Proc.jsp . Phys. Korolkov. J. Schmidt. Rev. 106. Mandelshtam and H. Chem. 8 E. 6246 1999 .-D. Gerber. Neumark. Schoendorff. Narevicius and N. Phys. Bargheer.org/jcp/copyright. Gutzwiller. S. Phys. 250 1998 . 1979 1967 . V. V. Chem. No. Lett. Brewer. H. Meyer. 112. Wang. Niv. Yourshaw. ACKNOWLEDGMENTS This work has been supported by the Center for Complex Molecular Systems and Biomolecules. 5733 2001 . B. Roeselova. B. Chem. 178 1928 . 9 M. Heller. L. A. 12 O. L. Rev. and P. and N. Horenko. Y. Jungwirth and R. and P. Moiseyev. Meyer. Manopoulos. S. J. Chem. H. Schwentner. Cederbaum. W. Narevicius. Rev.C. 1665 1984 .J. M. 2770 2001 . Taylor. Miller. 12229 2002 . 1 P. Phys. Jungwirth and R. 16 M. Chaban. 17 J. Manthe. J. Chem. and N. Phys. 3274 1997 . 28 V. 73 1990 . S. B. 2611 1990 . 186 1981 . 4412 1996 . and B. 11 G. 1583 1999 . and L. LNO0A032 . U. Europhys. and P. Phys. Phys. 115. V. Chem. J. Lett. J. Schmidt. Guhr. B. Z4 055 905.1. M. A 105. Mucha. M. Schutte. 20 P. J. J. Neuhauser. J. 65. Pullen and A. Phys. Chem. 25 E. 93. Pang and D. Chem. Downloaded 14 Jan 2005 to 132. Chem. 23 P. H. 5 P. Phys. J. Phys.aip. B. J. 26 D. 1289 1976 . 53. 13. Moiseyev. J. 75. 110. 4 P. 324 1996 .-D. Phys. D. H. 13 I.. Zhao. 23. Chem. Chem. Neuhauser. Phys. Lett. Edmonds. 4832 1997 . Rev. Phys. 115. A 106. Chem. Cederbaum. 105. Chem.29. Koppel. 162 1997 . Phys. H. H. 22 X. Chem. 280. J. Neuhauser. 252. 44. B. 10608 2001 . Jungwirth. 2 I. 105. Chem. 263. Lett. S. Haller. Phys. Jungwirth. H. Phys. Y. which is funded by the Czech Ministry of Education Grant No. M. Zdanska. and completed within the framework of the research project Grant No. 6046 1995 . L477 1981 . Lett. 27 J. Natl. M. J.A. 250 1997 . Lett. 21 S. 14 J. Schmidt. Lett. 14. Chem. Van Vleck. J. Miller. the preliminary discussion of this problem is found in Ref. Gerber. Heller. and C.
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