Finite temperature vibronic spectra of harmonic surfaces: a time-dependent coupled cluster approach

Reddy, Ch. Sridhar; Prasad, M. Durga

doi:10.1080/00268976.2015.1070928

Cited by 17 publications

(16 citation statements)

References 68 publications

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“…In the last years, diverse methods for first-principle spectrum simulations have been proposed [5][6][7][8][9][10], leading to high accurate predictions of band shapes, including their vibrational resolution [11]. Through simulations of vibrationally resolved absorption spectra of several molecules, Avila Ferrer et al [3] confirmed the existence of the redshift and suggested to compare vertical excitations not to the band maximum but to the first moment M 1 (center of gravity) of the absorption band.…”

Section: Introductionmentioning

confidence: 99%

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption

et al. 2020

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The analysis of the photoabsorption spectra of molecules shows that the band maximum is usually redshifted in comparison to the vertical excitation. We conducted a throughout analysis of this shift based on low-dimensional analytical and numerical model systems, showing that its origin is rooted in the frequency change between the ground and the excited states in multidimensional systems. Moreover, we deliver a benchmark of ab initio results for the shift based on a comparison of vertical excitations and band maxima calculated with the nuclear ensemble approach for the 28 organic molecules in the Mülheim molecular dataset. The mean value of the shift calculated over 60 transitions is 0.11 ± 0.08 eV. The mean value of the band width is 0.32 ± 0.14 eV.

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Section: Introductionmentioning

confidence: 99%

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption

et al. 2020

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“…TFD was introduced in the 1970s to provide a finite temperature representation of quantum mechanics within the wave‐function formalism 22 . While it had a deep impact on many problems of theoretical physics, 23–26 it did not receive much attention in molecular quantum dynamics: the first applications were reported relatively recently 27,28 and their number increased slowly ever since 29–33 …”

Section: Introductionmentioning

confidence: 99%

Finite temperature quantum dynamics of complex systems: Integrating thermo‐field theories and tensor‐train methods

Borrelli

Gelin

2021

WIREs Comput Mol Sci

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This review provides the fundamental theoretical tools for the development of a complete wave‐function formalism for the study of time‐evolution of chemico‐physical systems at finite temperature. The methodology is based on the non‐equilibrium thermo‐field dynamics (NE‐TFD) representation of quantum mechanics, which is alternative to the commonly used density matrix representation. TFD concepts are extended and integrated with the tensor‐train (TT) numerical tools leading to a novel and powerful theoretical and computational framework for the study of complex quantum dynamical problems. In addition, NE‐TFD techniques are extended to enable the study of dissipative open systems via a new formulation of the hierarchical equations of motion (HEOM) fully integrated with TT methodologies. We demonstrate that the combination of the TFD machinery with computational advantages of TTs results in a powerful theoretical and computational framework for scrutinizing dynamics of complex multidimensional electron‐vibrational systems. We illustrate the validity and the computational advantages of the developed methodologies by applying them to the study of quantum coherence effects in the energy‐transfer processes in antenna systems, to the analysis of fingerprints of vibrational modes in electron‐transfer and charge‐transfer processes in various model and realistic multidimensional molecular systems, as well as to simulation of other fundamental models of physical chemistry. This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Theoretical and Physical Chemistry > Statistical Mechanics

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“…In TFD, the density operator is linked to pure thermofield states evolving in time according to a Schrödinger type equation of motion, which replaces the Liouville-von Neumann equation on an artificially extended Hilbert space. Although TFD plays an important role in theoretical physics [13][14][15][16] , it has only recently entered the field of chemical physics [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] , where it has been combined with tensor trains/matrix product states (TT/MPS) 19,24,30,31 and the multi-Davydov D2 ansatz 22 to tackle the "curse of dimensionality" issue.…”

Section: Introductionmentioning

confidence: 99%

A Thermofield-based Multilayer Multiconfigurational Time-Dependent Hartree Approach to Non-Adiabatic Quantum Dynamics at Finite Temperature

Fischer,

Saalfrank

2021

Preprint

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We introduce a thermofield-based formulation of the multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) method to study finite temperature effects on non-adiabatic quantum dynamics from a non-stochastic, wave-function perspective. Our approach is based on the formal equivalence of bosonic many-body theory at zero temperature with doubled number of degrees of freedom and the thermal quasi-particle representation of bosonic thermofield dynamics (TFD). This equivalence allows for a transfer of bosonic many-body MCTDH as introduced by Wang and Thoss to the finite temperature framework of thermal quasi-particle TFD. As an application, we study temperature effects on the ultrafast internal conversion dynamics in pyrazine. We show, that finite temperature effects can be efficiently accounted for in the construction of multilayer expansions of thermofield states in the framework presented herein. Further, we find our results to agree well with existing studies on the pyrazine model based on the ρMCTDH method.

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Finite temperature vibronic spectra of harmonic surfaces: a time-dependent coupled cluster approach

Cited by 17 publications

References 68 publications

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption

Finite temperature quantum dynamics of complex systems: Integrating thermo‐field theories and tensor‐train methods

A Thermofield-based Multilayer Multiconfigurational Time-Dependent Hartree Approach to Non-Adiabatic Quantum Dynamics at Finite Temperature

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