A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy
We present an approach for calculating nonlinear spectroscopic observables, which overcomes the approximations inherent to current phenomenological models without requiring the computational cost of performing molecular dynamics simulations. The trajectory mapping method uses the semi-classical appr...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Institute of Physics (AIP)
2012
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| Online Access: | http://hdl.handle.net/1721.1/73991 https://orcid.org/0000-0002-6101-4145 |
| _version_ | 1811073451317788672 |
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| author | Ramasesha, Krupa De Marco, Luigi Horning, Andrew Davis Mandal, Aritra Tokmakoff, Andrei |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Ramasesha, Krupa De Marco, Luigi Horning, Andrew Davis Mandal, Aritra Tokmakoff, Andrei |
| author_sort | Ramasesha, Krupa |
| collection | MIT |
| description | We present an approach for calculating nonlinear spectroscopic observables, which overcomes the approximations inherent to current phenomenological models without requiring the computational cost of performing molecular dynamics simulations. The trajectory mapping method uses the semi-classical approximation to linear and nonlinear response functions, and calculates spectra from trajectories of the system's transition frequencies and transition dipole moments. It rests on identifying dynamical variables important to the problem, treating the dynamics of these variables stochastically, and then generating correlated trajectories of spectroscopic quantities by mapping from the dynamical variables. This approach allows one to describe non-Gaussian dynamics, correlated dynamics between variables of the system, and nonlinear relationships between spectroscopic variables of the system and the bath such as non-Condon effects. We illustrate the approach by applying it to three examples that are often not adequately treated by existing analytical models – the non-Condon effect in the nonlinear infrared spectra of water, non-Gaussian dynamics inherent to strongly hydrogen bonded systems, and chemical exchange processes in barrier crossing reactions. The methods described are generally applicable to nonlinear spectroscopy throughout the optical, infrared and terahertz regions. |
| first_indexed | 2024-09-23T09:33:19Z |
| format | Article |
| id | mit-1721.1/73991 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:33:19Z |
| publishDate | 2012 |
| publisher | American Institute of Physics (AIP) |
| record_format | dspace |
| spelling | mit-1721.1/739912022-09-30T15:15:37Z A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy Ramasesha, Krupa De Marco, Luigi Horning, Andrew Davis Mandal, Aritra Tokmakoff, Andrei Massachusetts Institute of Technology. Department of Chemistry Tokmakoff, Andrei Ramasesha, Krupa De Marco, Luigi Horning, Andrew Davis Mandal, Aritra Tokmakoff, Andrei We present an approach for calculating nonlinear spectroscopic observables, which overcomes the approximations inherent to current phenomenological models without requiring the computational cost of performing molecular dynamics simulations. The trajectory mapping method uses the semi-classical approximation to linear and nonlinear response functions, and calculates spectra from trajectories of the system's transition frequencies and transition dipole moments. It rests on identifying dynamical variables important to the problem, treating the dynamics of these variables stochastically, and then generating correlated trajectories of spectroscopic quantities by mapping from the dynamical variables. This approach allows one to describe non-Gaussian dynamics, correlated dynamics between variables of the system, and nonlinear relationships between spectroscopic variables of the system and the bath such as non-Condon effects. We illustrate the approach by applying it to three examples that are often not adequately treated by existing analytical models – the non-Condon effect in the nonlinear infrared spectra of water, non-Gaussian dynamics inherent to strongly hydrogen bonded systems, and chemical exchange processes in barrier crossing reactions. The methods described are generally applicable to nonlinear spectroscopy throughout the optical, infrared and terahertz regions. United States. Dept. of Energy (Grant DE-FG02-99ER14988) 2012-10-15T19:48:40Z 2012-10-15T19:48:40Z 2012-04 2012-01 Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/73991 Ramasesha, Krupa et al. “A Phenomenological Approach to Modeling Chemical Dynamics in Nonlinear and Two-dimensional Spectroscopy.” The Journal of Chemical Physics 136.13 (2012): 134507. Web. https://orcid.org/0000-0002-6101-4145 en_US http://dx.doi.org/10.1063/1.3700718 Journal of Chemical Physics Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf American Institute of Physics (AIP) Prof. Tokmakoff via Erja Kajosalo |
| spellingShingle | Ramasesha, Krupa De Marco, Luigi Horning, Andrew Davis Mandal, Aritra Tokmakoff, Andrei A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title | A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title_full | A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title_fullStr | A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title_full_unstemmed | A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title_short | A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy |
| title_sort | phenomenological approach to modeling chemical dynamics in nonlinear and two dimensional spectroscopy |
| url | http://hdl.handle.net/1721.1/73991 https://orcid.org/0000-0002-6101-4145 |
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