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Modeling vibrational dephasing and energy relaxation of intramolecular anharmonic modes for multidimensional infrared spectroscopies
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10.1063/1.2244558
/content/aip/journal/jcp/125/8/10.1063/1.2244558
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/8/10.1063/1.2244558
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

The double-sided Feynman diagrams contributing to the (a) rephasing and (b) nonrephasing Liouville space pathways. The variables represent the delays between the three input pulses to generate a third-order nonlinear polarization.

Image of FIG. 2.
FIG. 2.

Schematic illustrations of effects of (a) the linear-linear (LL) and (b) the square-linear (SL) system-bath couplings on an anharmonic potential. The black lines represent the unperturbed potential, while the colored lines the perturbed ones. LL coupling swings the position of the potential minimum and deforms the potential, whereas SL coupling alters the curvature of the potential. Hence, both couplings induce the frequency fluctuation. Note that the LL and SL couplings mainly cause the one- and two-quantum transitions, respectively, as can be seen from the system-bath coupling expressed by the one-quantum creation and annihilation operators and .

Image of FIG. 3.
FIG. 3.

(Color) 2D-IR correlation spectra of the Morse oscillator (, ) in the motional narrowing regime. The spectra were calculated from (a) the LTC-QFP approach with Eq. (3.8) and (b) the stochastic approach with Eq. (2.11) with the coupling strength and the amplitude of fluctuation adjusted by Eq. (3.18). The panels from the top to bottom show the signals for (i) LL, (ii) SL, (iii) , and (iv) system-bath coupling cases, respectively. The noise correlation time is in the motional narrowing regime . The negative-going peaks arise from the 0-1 transition, whereas the positive-going peaks from the 1-2 transition.

Image of FIG. 4.
FIG. 4.

Linear absorption spectra calculated from Eq. (4.9) for the Markovian noise case and the white noise case . We set the system-bath coupling strength for both to . The normalization of each spectrum is such that the maximum of the spectrum for the Markovian case is unity.

Image of FIG. 5.
FIG. 5.

(Color) 2D-IR correlation spectra of the Morse oscillator (, ) in the spectral diffusion regime. The spectra were calculated from (a) the LTC-QFP approach with Eq. (3.8) and (b) the stochastic approach with Eq. (2.11). The panels from the top to bottom show the spectra for (i) LL, (ii) SL, (iii) , and (iv) system-bath coupling cases, respectively. The inverse noise correlation time is . The negative-going peaks arise from the 0-1 transition, whereas the positive-going peaks from the 1-2 transition.

Image of FIG. 6.
FIG. 6.

Applicability of various approaches. The low-temperature corrected quantum Fokker-Planck (LTC-QFP) equation [Eq. (3.8)] reduces to the Gaussian-Markovian quantum Fokker-Planck (GM-QFP) equation at high temperature (Refs. 11, 39, 75, and 82). When the two conditions and are satisfied simultaneously, the LTC-QFP and GM-QFP agree with the results from the stochastic theory besides the effects of blueshifts due to the dissipation with the finite noise correlation time.

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/content/aip/journal/jcp/125/8/10.1063/1.2244558
2006-08-22
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Modeling vibrational dephasing and energy relaxation of intramolecular anharmonic modes for multidimensional infrared spectroscopies
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/8/10.1063/1.2244558
10.1063/1.2244558
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