Finite-temperature vibronic spectra from the split-operator coherence thermofield dynamics
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arXiv
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| Format: | Preprint |
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2023
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| _version_ | 1866913240985894912 |
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| author | Zhang, Zhan Tong Vaníček, Jiří J. L. |
| author_facet | Zhang, Zhan Tong Vaníček, Jiří J. L. |
| contents | We present a numerically exact approach for evaluating vibrationally resolved electronic spectra at finite temperatures using the coherence thermofield dynamics. In this method, which avoids implementing an algorithm for solving the von Neumann equation for coherence, the thermal vibrational ensemble is first mapped to a pure-state wavepacket in an augmented space, and this wavepacket is then propagated by solving the standard, zero-temperature Schrödinger equation with the split-operator Fourier method. We show that the finite-temperature spectra obtained with the coherence thermofield dynamics in a Morse potential agree exactly with those computed by Boltzmann-averaging the spectra of individual vibrational levels. Because the split-operator thermofield dynamics on a full tensor-product grid is restricted to low-dimensional systems, we briefly discuss how the accessible dimensionality can be increased by various techniques developed for the zero-temperature split-operator Fourier method. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2311_10004 |
| institution | arXiv |
| publishDate | 2023 |
| record_format | arxiv |
| spellingShingle | Finite-temperature vibronic spectra from the split-operator coherence thermofield dynamics Zhang, Zhan Tong Vaníček, Jiří J. L. Chemical Physics Computational Physics Quantum Physics We present a numerically exact approach for evaluating vibrationally resolved electronic spectra at finite temperatures using the coherence thermofield dynamics. In this method, which avoids implementing an algorithm for solving the von Neumann equation for coherence, the thermal vibrational ensemble is first mapped to a pure-state wavepacket in an augmented space, and this wavepacket is then propagated by solving the standard, zero-temperature Schrödinger equation with the split-operator Fourier method. We show that the finite-temperature spectra obtained with the coherence thermofield dynamics in a Morse potential agree exactly with those computed by Boltzmann-averaging the spectra of individual vibrational levels. Because the split-operator thermofield dynamics on a full tensor-product grid is restricted to low-dimensional systems, we briefly discuss how the accessible dimensionality can be increased by various techniques developed for the zero-temperature split-operator Fourier method. |
| title | Finite-temperature vibronic spectra from the split-operator coherence thermofield dynamics |
| topic | Chemical Physics Computational Physics Quantum Physics |
| url | https://arxiv.org/abs/2311.10004 |