The semiclassical way to molecular spectroscopy

Heller, Eric J.

doi:10.1021/ar00072a002

Cited by 1,415 publications

(838 citation statements)

References 21 publications

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“…In this ͑theoretical͒ limit the laser pulse simply promotes to the excited electronic state a replica of the initial nuclear state-times the transition dipole moment of the electronic transition-which then evolves under field-free conditions ͑a Franck-Condon wave packet͒. 16,17 This provides a simple picture of the photoinduced dynamics and it can be shown that the branching ratio dictated by the Franck-Condon wave packet is identical to the branching ratio obtained by a cw laser, when the full absorption band is scanned uniformly over all frequencies. 9 In fact, the dynamics created by any laser-pulse shape-in the weak-field ͑first-order perturbation theory͒ limit-can be described as a superposition of Franck-Condon wave packets excited at different times.…”

Section: ͑1͒mentioning

confidence: 99%

Isotope effects in the photofragmentation of symmetric molecules: The branching ratio of OD∕OH in water

Henriksen

Møller

Engel

2005

The Journal of Chemical Physics

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With HOD initially in its vibrational ground state, we present a new detailed interpretation of the OD∕OH branching ratio (∼3) in the photoinduced process D+OH←HOD→H+OD, in the first absorption band. Using semiclassical arguments, we show that the branching ratio has little to do with the initial distribution of configurations, but the initial momentum distribution plays a key role in determination of the branching ratio. The formation of D+OH arises from initial situations where OD is stretching, and it stretches faster than OH, whereas all other motions lead to H+OD. This picture is confirmed by quantum wave-packet calculations.

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Section: ͑1͒mentioning

confidence: 99%

Isotope effects in the photofragmentation of symmetric molecules: The branching ratio of OD∕OH in water

Henriksen

Møller

Engel

2005

The Journal of Chemical Physics

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“…In order to do so, we first calculate the a 1g vibrational envelope of the first absorption band assuming one single electronic origin, 5 f 3 1 ⌫ 8u ( 4 I 9/2 )→ 5 f 2 6d(t 2g ) 1 1 ⌫ 8g ( 4 K 11/2 ). ͓We use the semiclassical time-dependent approach of Heller, 50,51 with bond distances and a 1g vibrational frequencies taken from Table IV. Detailed formulas can be found in Refs.…”

Section: àmentioning

confidence: 99%

Ab initio theoretical studies on U3+ and on the structure and spectroscopy of U3+ substitutional defects in Cs2NaYCl6, 5f 26d1 manifold

Seijo

Barandiarán

2003

The Journal of Chemical Physics

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In this paper we present the results of spin-orbit relativistic ab initio model potential embedded cluster calculations of the 5 f 2 6d 1 excited manifold of (UCl 6 ) 3Ϫ embedded in a reliable representation of the Cs 2 NaYCl 6 elpasolite host. They are aimed at interpreting the 5 f 3 →5 f 2 6d 1 absorption bands reported by Karbowiak et al. ͓J. Chem. Phys. 108, 10181 ͑1998͒.͔ An excellent agreement is found between the calculated energies of the absorption transitions from the ground state 5 f 3 1 ⌫ 8u ( 4 I 9/2 ) and the experimental data, which supports a detailed interpretation of the electronic nature of the absorption spectrum in the energy region 14 000-23 000 cm Ϫ1 . In particular, the three unidentified electronic origins that had been experimentally detected are now assigned, and the observed bands are interpreted as having multiple electronic origins. From the structural point of view, the excited states of the 5 f 2 6d 1 manifold are classified in two sets of main configuration 5 f 2 6d(t 2g ) 1 and 5 f 2 6d(e g ) 1 with bond distances R e ͓5 f 2 6d(t 2g ) 1 ͔ϽR e ͓5 f 3 ͔ ϽR e ͓5 f 2 6d(e g ) 1 ͔. The energies of the 5 f 2 6d 1 manifold of free U 3ϩ have also been calculated; experimental data on them are not available in the literature to the best of our knowledge. These results contribute to show that wave function based ab initio methods can provide useful structural and spectroscopic information, complementary to the experimental data, in studies on actinide ion impurities doping ionic hosts, where large manifolds of 5d nϪ1 6d 1 excited states are involved.

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“…The involvement of indirect modes appears as an individual band in the spectrum and is interpreted as resonance in the time-independent approach and recurrence in the time-dependent picture. Recurrence appears as peaks in the norm of the autocorrelation function in the time domain and the Fourier transformation of the autocorrelation function produces the spectrum in the energy domain [55] as shown in the right-lower part of Figure 1. These are included in most theoretical studies for moderately small molecules by using the wave-packet propagation method (X-NO stands for the molecules like Cl-NO, HO-NO, and CH 3 O-NO, etc.…”

Section: (6) Analysis Of the Propagated Resultsmentioning

confidence: 99%

Basics of the time‐dependent wave‐packet propagation for photodissociations of polyatomic systems

Baeck

2016

Int J of Quantum Chemistry

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A brief background on the quantum wave-packet propagation method for the study of photodissociation dynamics of polyatomic molecules is summarized as a short tutorial review. The main emphasis is on reasons to use the wave-packet propagation method, followed by a description about basic considerations for practical application of the wave-packet method to polyatomic molecules. The considerations are divided into six steps in the following sequence: (1) prerequisite information for related states, (2) search for critical points, (3) selection of coordinates and kinetic energy operator, (4) potential energy surface, (5) propagation of wave-packet, and (6) analysis of the propagated results. Limitations of the present review and a very brief perspective are given as concluding remarks.

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The semiclassical way to molecular spectroscopy

Cited by 1,415 publications

References 21 publications

Isotope effects in the photofragmentation of symmetric molecules: The branching ratio of OD∕OH in water

Isotope effects in the photofragmentation of symmetric molecules: The branching ratio of OD∕OH in water

Ab initio theoretical studies on U3+ and on the structure and spectroscopy of U3+ substitutional defects in Cs2NaYCl6, 5f 26d1 manifold

Basics of the time‐dependent wave‐packet propagation for photodissociations of polyatomic systems

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