Signatures of Nanoconfinement on the Linear and Nonlinear Vibrational Spectroscopy of a Model Hydrogen-Bonded Complex Dissolved in a Polar Solvent

Tomkins, Joseph; Hanna, Gabriel

doi:10.1021/jp407469f

Cited by 1 publication

(2 citation statements)

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“…While Geva et al 37−39 and Hanna 40,41 have applied MQCLE to calculate vibrational spectra in MQC environment, Hanna 42,43 calculated Optical response function to probe electron transfer dynamics using the basis mapping technique developed by Nassimi and Kapral. 44 However, the path to the end results, approach, purpose, rigor, applications, and results differ from those reported by Toutounji.…”

Section: Introductionmentioning

confidence: 99%

“…The response function approach has been widely utilized in calculating spectroscopic signals to probe systems of interest. , For example, Staib and Borgis employed quantum-classical dynamics to compute IR spectra of OH stretch mode spectra of hydrogen-bonded methanol complexes dissolved in carbon tetrachloride are computed; however, MQCLE was never used in their simulation and no electronic spectra were reported. While Geva et al − and Hanna , have applied MQCLE to calculate vibrational spectra in MQC environment, Hanna , calculated Optical response function to probe electron transfer dynamics using the basis mapping technique developed by Nassimi and Kapral . However, the path to the end results, approach, purpose, rigor, applications, and results differ from those reported by Toutounji. − ,− The optical response function developed by Hanna , to probe electron transfer dynamics seems to neglect frequency change (excited state vibrational force constant change) and anharmonicity upon electronic excitation, and they do not seem to offer in-depth spectroscopic analysis, especially with respect to electronic dephasing, electron–phonon coupling, shape, and symmetry of spectral profiles, all of which mark differences compared to MQCD-based report reviewed herein.…”

Section: Introductionmentioning

confidence: 99%

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Mixed Quantum-Classical Liouville Equation Treatment of Electronic Spectroscopy of Condensed Systems: Harmonic and Anharmonic Electron–Phonon Coupling

Toutounji

2023

J. Chem. Theory Comput.

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This Review integrates the use of electronic optical response function theory and the mixed quantum-classical (MQC) Liouville equation (MQCLE), thereby leading to electronic spectroscopy in MQC media. It further sheds light on the applicability, utility, and efficiency of the mixed quantum-classical dynamics (MQCD) formalism, which starts off with the MQCLE, in probing spectroscopy and dynamics of condensed systems, whereby quantum mechanics and classical mechanics are combined systematically. The author has been exploring and implementing MQCD to investigate electron−phonon coupling effects on electronic dephasing in harmonic and anharmonic systems by calculating linear and nonlinear optical transition analytically and numerically dipole moment time correlation functions in an MQC environment, thereby presenting an in depth spectral profile analysis and their shape and symmetry. The distinctive capability of the MQC time correlation functions is that ergodicity and stationarity properties are inherently satisfied as part of the mixed quantum-classical dynamics (MQCD) framework, unlike classical correlation functions. While some research groups have applied MQCLE to calculate vibrational spectra to study hydrogen-bonded complexes in a MQC environment and other groups calculated Optical response function to probe electron transfer dynamics using the basis mapping technique, the approach, purpose, rigor, applications, and path to the end results reported herein are different. Finally, the same framework is employed to study dissipative systems in the MQC limit, whereby the zerophonon line adopts the correct width and eliminates its asymmetry. While the full quantum mechanical model, like the multimode Brownian oscillator (MBO) model, yields the correct width and inaccurate shape in the low-temperature limit, the MQCD formalism seems to produce an accurate zero-phonon profile. Nonlinear optical signals are also reviewed in MQC media to show the applicability and utility of this approach. The vibronic optical response functions developed here will account for geometry change, frequency change, and anharmonicity upon electronic excitation to accurately probe electronic dephasing, electron−phonon coupling, shape, and symmetry of profiles and present differences and similarities to the MBO model on pure electronic dephasing. Frequency change and anharmonicity are vitally crucial for accurately assessing electron−phonon coupling upon electronic excitation. This is an additional unique result obtained by the author to further demonstrate the applicability and utility of this approach over other approximation schemes in probing electronic dephasing including that of the MBO model.

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