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Potential energy curves and spectroscopic parameters of the diatomic silver anion and neutral silver dimer
Description
The process of a two-channel decay of the diatomic silver anion (Ag2-), namely the spontaneous electron ejection giving Ag2 + e- and the dissociation leading to Ag- + Ag is theoretically studied. The ground state potential energy curves (PECs) of the neutral silver dimer and anionic silver diatomic molecule are calculated using the single reference coupled-cluster method with singles and doubles, and perturbative triples (CCSD(T)). The proper pseudopotential and optimized basis set are used in the presented approach. The interaction energies are corrected for the basis set superposition error (BSSE) by counterpoise (CP) correction. Based on the energies of rovibrational levels calculated using PECs, we are able to characterize the decay channels and compare our results with the experimental data. Having the ground state PEC of an anionic system, we calculate the quantum dynamics (QD) of the dissociation process, which allows us to calculate the widths and lifetimes of highly-lying rovibrational levels. The predissociation lifetimes for quasibond states with small widths of levels are treated with a time-independent approach. We also present the non-adiabatic coupling matrix element between chosen initial and final vibrational states of Ag2- and Ag2, which allow us to estimate the spontaneous electron emission lifetimes.
The dataset contains five files in csv format: two potential energy curves for neutral silver dimer (Ag2_1sSg_CC_CP_5Z.csv) and diatomic silver anion (Ag2-_1dSu_CC_CP_5Z.csv), as well as spectroscopic parametres for these potentials (Ag2_spectroscopic_parameters.csv, Ag2-_spectroscopic_parameters.csv) with Ag2 electron affinities as additional column in spectroscopic parameters file and separate file for electon affinity of the Ag atom (Ag_atom_electron_affinities.csv). Potential energy curves were calculated with cusotm basis set of 5Z quality, as well as original aV5Z/awCV5Z basis set of Peterson and Puzzarini (denoted by PP), using CCSD(T) method. Results for additional calculations using two theory levels, namely MRCI and CCSD(T), and including counterpoise (CP) correction, as well as additional midbond (MB) basis functions, are shown in the spectroscopic parameters file. First line in each file denotes the columns and units, with R corresponding to internuclear distance (in a0 – unit of length in atomic units), E to energy (in hartree – unit of energy in atomic units), Re to the equilibrium internuclear distance (in Angstroms), D_e to the well depth of the potential (in cm^(-1)), D_0 to the zero point energy (in cm^(-1)), omega_e to the vibrational wavenumber (in cm^(-1)), B_e to the equilibrium rotational constant (in cm^(-1)) and EA (in cm^(-1)) to electron affinity.
Dataset file
hexmd5(md5(part1)+md5(part2)+...)-{parts_count} where a single part of the file is 512 MB in size.Example script for calculation:
https://github.com/antespi/s3md5
File details
- License:
-
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CC BY-NC-SANon-commercial - Share-alike
Details
- Year of publication:
- 2021
- Verification date:
- 2021-04-15
- Dataset language:
- English
- Fields of science:
-
- physical sciences (Natural sciences)
- chemical sciences (Natural sciences)
- DOI:
- DOI ID 10.34808/kf1h-nq07 open in new tab
- Series:
- Verified by:
- Gdańsk University of Technology
Keywords
- Ag2
- Ag2-
- silver dimer
- nonadiabatic coupling
- potential energy curves
- rovibrational predissociation
- continuum orbitals
- spontaneous electron emission
- lifetime
- quantum dynamics
- CCSD(T) method
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