Simplified Sum-Over-States Approach for Predicting Resonance Raman Spectra. Application to Nucleic Acid Bases

Rappoport, Dmitrij; Shim, Sangwoo; Aspuru‐Guzik, Alán

doi:10.1021/jz200413g

Cited by 26 publications

(23 citation statements)

References 59 publications

(139 reference statements)

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“…The results of both approaches have been compared by Kane and Jensen using the examples of uracil, rhodamine 6G, and an iron complex. 19 Other formulations based on the vibronic theory have recently been described by Rappoport et al 20 and Santoro et al 21 A basically different approach was taken by Jensen and Schatz. 22 Their method is similar to Placzek's polarizability theory, which nowadays is available in many quantum chemical software packages for the calculation of non-resonant Raman spectra.…”

Section: Introductionmentioning

confidence: 99%

Resonance Raman spectra of ortho-nitrophenol calculated by real-time time-dependent density functional theory

Thomas

Latorre

Marquetand

2013

The Journal of Chemical Physics

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A new approach for the calculation of resonance Raman spectra is presented. The new method is based on dynamic polarizabilities from real-time time-dependent density functional theory, and its estimations are compared to two established techniques for the prediction of resonance Raman spectra. These established methods either use dynamic polarizabilities from linear-response time-dependent density functional theory or employ excited-state gradients. The three different ways to calculate resonance Raman spectra are investigated using the example of ortho-nitrophenol. The three methods give very similar results, respectively, for the four different exchange-correlation functionals applied. Thus, the new approach is validated for the calculation of resonance Raman intensities and advantages as well as disadvantages are discussed.

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Section: Introductionmentioning

confidence: 99%

Resonance Raman spectra of ortho-nitrophenol calculated by real-time time-dependent density functional theory

Thomas

Latorre

Marquetand

2013

The Journal of Chemical Physics

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“…We deliberately skip all the mathematical aspects describing the resonance Raman effect, which are well documented in the literature. [42][43][44][45] In the case of a resonantly excited transition from initial ground electronic state jii to excited electronic state jfi, implementing the sum-over-state approach, 46 the polarizability tensor [a qr ] if is the result of four contributions referred to as A, B, C, and D terms. Of these, the A and B terms are given by 42,43 the following expressions:…”

Section: Theory Of Resonance Raman Scatteringmentioning

confidence: 99%

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

2011

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The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single "do-it-all" technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-μs) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

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“…18, [22][23][24][25] More recently, chemists have also incorporated electronic structure theories into the semiclassical description of Raman spectroscopy. [26][27][28][29] In general, because it relies on a sum over all states (nuclear and electronic), the KHD formalism can be difficult to implement in practice.…”

Section: Introductionmentioning

confidence: 99%

Ehrenfest+R dynamics. II. A semiclassical QED framework for Raman scattering

Chen

Sukharev

et al. 2019

The Journal of Chemical Physics

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In a previous paper [], we introduced Ehrenfest+R dynamics for a two-level system and showed how spontaneous emission can be heuristically included such that, after averaging over an ensemble of Ehrenfest+R trajectories, one can recover both coherent and incoherent electromagnetic fields. In the present paper, we now show that Ehrenfest+R dynamics can also correctly describe Raman scattering, whose features are completely absent from standard Ehrenfest dynamics. Ehrenfest+R dynamics appear to be quantitatively accurate both for resonant and off-resonant Raman signals, as compared with Kramers-Heisenberg-Dirac (KHD) theory.

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Simplified Sum-Over-States Approach for Predicting Resonance Raman Spectra. Application to Nucleic Acid Bases

Cited by 26 publications

References 59 publications

Resonance Raman spectra of ortho-nitrophenol calculated by real-time time-dependent density functional theory

Resonance Raman spectra of ortho-nitrophenol calculated by real-time time-dependent density functional theory

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

Ehrenfest+R dynamics. II. A semiclassical QED framework for Raman scattering

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