Time-Dependent Relativistic Two-Component Equation-of-Motion Coupled-Cluster for Open-Shell Systems: TD-EA/IP-EOMCC
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arXiv
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| Format: | Preprint |
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2026
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| author | Pathirage, P. D. Varuna S. Yuwono, Stephen H. Li, Xiaosong DePrince III, A. Eugene |
| author_facet | Pathirage, P. D. Varuna S. Yuwono, Stephen H. Li, Xiaosong DePrince III, A. Eugene |
| contents | We present a combined imaginary-time/real-time time-dependent (TD) approach for evaluating linear absorption spectra of open-shell systems at the electron attachment (EA) and ionization potential (IP) equation-of-motion coupled-cluster (EOMCC) levels of theory and within the exact two-component relativistic framework. The absorption lineshape is given by the Fourier transform of the electric dipole autocorrelation function, which is obtained from a real-time simulation. Approximations of the lowest-energy EA- and IP-EOMCC eigenstates, which are required as initial states for the real-time simulation, are generated by propagating a Koopmans EA/IP state in imaginary time. TD-EA/IP-EOMCC linear absorption spectra of open-shell atomic (Na, K, Rb, F, Cl, and Br) and diatomic (SiH and ClO) systems closely reproduce those obtained from standard TD-EA/IP procedures carried out in the frequency domain. We find that the existence of low-lying states with non-negligible overlap with the Koopmans determinant impacts the length of the imaginary-time propagation required to obtain an initial state that produces correct absolute energies and peak height intensities in spectra extracted from the subsequent real-time TD-EA/IP-EOMCC calculations. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2602_00985 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Time-Dependent Relativistic Two-Component Equation-of-Motion Coupled-Cluster for Open-Shell Systems: TD-EA/IP-EOMCC Pathirage, P. D. Varuna S. Yuwono, Stephen H. Li, Xiaosong DePrince III, A. Eugene Chemical Physics We present a combined imaginary-time/real-time time-dependent (TD) approach for evaluating linear absorption spectra of open-shell systems at the electron attachment (EA) and ionization potential (IP) equation-of-motion coupled-cluster (EOMCC) levels of theory and within the exact two-component relativistic framework. The absorption lineshape is given by the Fourier transform of the electric dipole autocorrelation function, which is obtained from a real-time simulation. Approximations of the lowest-energy EA- and IP-EOMCC eigenstates, which are required as initial states for the real-time simulation, are generated by propagating a Koopmans EA/IP state in imaginary time. TD-EA/IP-EOMCC linear absorption spectra of open-shell atomic (Na, K, Rb, F, Cl, and Br) and diatomic (SiH and ClO) systems closely reproduce those obtained from standard TD-EA/IP procedures carried out in the frequency domain. We find that the existence of low-lying states with non-negligible overlap with the Koopmans determinant impacts the length of the imaginary-time propagation required to obtain an initial state that produces correct absolute energies and peak height intensities in spectra extracted from the subsequent real-time TD-EA/IP-EOMCC calculations. |
| title | Time-Dependent Relativistic Two-Component Equation-of-Motion Coupled-Cluster for Open-Shell Systems: TD-EA/IP-EOMCC |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2602.00985 |