New determination of the adiabatic ionization potential of the BaOH radical from laser photoionization-molecular beam experiments and ab initio calculations

Rossa, Maximiliano; Cabanillas-Vidosa, Iván; Pino, Gustavo A.; Ferrero, Juan C.

doi:doi:10.1063/1.3682283

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Absorption by DNA single strands of adenine isolated in vacuo: The role of multiple chromophores

The degree of electronic coupling between DNA bases is a topic being up for much debate. Here we report on the intrinsic electronic properties of isolated DNA strands in vacuo free of solvent, which is a good starting point for high-level excited states calculations. Action spectra of DNA single strands of adenine reveal sign of exciton coupling between stacked bases from blueshifted absorption bands (∼3 nm) relative to that of the dAMP mononucleotide (one adenine base). The bands are blueshifte...

B(1)¹Π state of KCs: High-resolution spectroscopy and description of low-lying energy levels

The diode laser induced B(1)1Π → X1Σ+ fluorescence spectra of the KCs molecule were recorded by Fourier-transform spectrometer with resolution of 0.03 cm−1. Buffer gas Ar was used to facilitate appearance of rotation relaxation lines in the spectra, thus enlarging the B(1)1Π dataset, allowing one to determine the Λ-splitting constants and to reveal numerous local perturbations. A dataset was systematically obtained for B(1)1Π vibrational levels v′ ∈ [0; 5] nonuniformly covering rotational levels...

The adiabatic ionization potential of the BaOH radical, as generated in a laser vaporization-supersonic expansion source has been determined by laser photoionization experiments to be (4.55 ± 0.03) eV. This value supports the three lowest out of seven previous experimental estimates, the former ranging from 4.35 to 4.62 eV. The present result is compared to ab initio calculations, as performed using both quantum chemistry at different levels of theory and density functional theory, and trying several effective core potentials and their accompanying basis sets for Ba. The most satisfactory agreement is obtained for either the adiabatic or vertical ionization potentials that derive from post-Hartree-Fock [MP2 and CCSD(T)] treatments of electron correlation, along with consideration of relativistic effects and extensive basis sets for Ba, in both BaOH and BaOH⁺. Such conclusions extend to the results of related calculations on the Ba−OH dissociation energies of BaOH and BaOH⁺, which were performed to help in calibrating the present computational study. Bonding in BaOH/BaOH⁺, as well as possible sources of discrepancy with previous experimental determinations of the BaOH adiabatic ionization potential are discussed.

Article Outline

INTRODUCTION
EXPERIMENTAL
THEORETICAL METHODS
RESULTS AND DISCUSSION
CONCLUSIONS

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KEYWORDS and PACS

Keywords

ab initio calculations, barium compounds, bonds (chemical), coupled cluster calculations, density functional theory, dissociation energies, electron correlations, HF calculations, ionisation potential, molecular beams, molecule-photon collisions, perturbation theory, photoionisation, quantum chemistry, relativistic corrections

PACS

33.80.Eh

Autoionization, photoionization, and photodetachment
31.15.bw

Coupled-cluster theory
31.15.xp

Perturbation theory
31.15.xr

Self-consistent-field methods
33.15.Fm

Bond strengths, dissociation energies
33.15.Ry

Ionization potentials, electron affinities, molecular core binding energy

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3682283

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

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$abstract.society.value is a Member of CrossRef

American Institute of Physics

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