Ab Initio Excited-State Transient Raman Analysis

Alessio Petrone; David B. Williams-Young; David B. Lingerfelt; Xiaosong Li

doi:10.1021/acs.jpca.7b02905

Ab Initio Excited-State Transient Raman Analysis

Alessio Petrone, David B. Williams-Young, David B. Lingerfelt, Xiaosong Li

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

Time-resolved Raman spectroscopy has proven useful for studying the formation of polarons in conjugated polymers, verifying the presence of reactive intermediates in photochemical reactions, investigating nonradiative transitions in the short lifetime of the photoexcited species, and resolving electron-phonon coupling strengths and exciton dissociation in crystalline materials. In this paper, we present an excited state transient Raman analysis protocol combining ab initio direct molecular dynamics, transient excited state Hessian, and excited state nonresonant Raman activities evaluations. Prototypical molecules are used as test cases, showing the evolution of the transient Raman signatures that follow electronic excitation. This protocol provides a direct route to assigning the vibrations implicated in the (photo)dynamics of several (photoactive) systems, complementary to the transient infrared analysis.

Original language	English
Pages (from-to)	3958-3965
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	121
Issue number	20
DOIs	https://doi.org/10.1021/acs.jpca.7b02905
State	Published - May 25 2017
Externally published	Yes

Funding

The development of TDDFT second derivatives is supported by the U.S. Department of Energy (contract no. DESC0006863 to X.L.) The development of the transient vibrational spectral analysis protocol is supported by the National Science Foundation (Grant No. CHE-1565520). The application to studies of excited-state chemical process is supported by the Ultrafast Initiative of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DEAC02- 06CH11357. This work was facilitated though the use of advanced computational, storage, and networking infrastructure provided by the Hyak supercomputer system at the University of Washington, funded by the Student Technology Fee.

Funders	Funder number
Ultrafast Initiative
National Science Foundation	CHE-1565520, 1464497
U.S. Department of Energy	DESC0006863
Office of Science
Basic Energy Sciences
Argonne National Laboratory	DEAC02- 06CH11357
University of Washington

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abstract = "Time-resolved Raman spectroscopy has proven useful for studying the formation of polarons in conjugated polymers, verifying the presence of reactive intermediates in photochemical reactions, investigating nonradiative transitions in the short lifetime of the photoexcited species, and resolving electron-phonon coupling strengths and exciton dissociation in crystalline materials. In this paper, we present an excited state transient Raman analysis protocol combining ab initio direct molecular dynamics, transient excited state Hessian, and excited state nonresonant Raman activities evaluations. Prototypical molecules are used as test cases, showing the evolution of the transient Raman signatures that follow electronic excitation. This protocol provides a direct route to assigning the vibrations implicated in the (photo)dynamics of several (photoactive) systems, complementary to the transient infrared analysis.",

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AU - Lingerfelt, David B.

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AB - Time-resolved Raman spectroscopy has proven useful for studying the formation of polarons in conjugated polymers, verifying the presence of reactive intermediates in photochemical reactions, investigating nonradiative transitions in the short lifetime of the photoexcited species, and resolving electron-phonon coupling strengths and exciton dissociation in crystalline materials. In this paper, we present an excited state transient Raman analysis protocol combining ab initio direct molecular dynamics, transient excited state Hessian, and excited state nonresonant Raman activities evaluations. Prototypical molecules are used as test cases, showing the evolution of the transient Raman signatures that follow electronic excitation. This protocol provides a direct route to assigning the vibrations implicated in the (photo)dynamics of several (photoactive) systems, complementary to the transient infrared analysis.

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Ab Initio Excited-State Transient Raman Analysis

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