Journal ArticleDOI
Methylene: A study of the X̃ 3B1 and ã 1A1 states by photoelectron spectroscopy of CH−2 and CD−2
Doreen G. Leopold,Kermit K. Murray,Amy E. Stevens Miller,Amy E. Stevens Miller,W. C. Lineberger +4 more
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TLDR
In this article, a new flowing afterglow photoelectron spectrometer with improved energy resolution (11 meV) is presented for the CH2(X 3B1)+e−e−←CH−2 (X 2B1) transitions of the methylene and perdeuterated methylene anions, with an electron affinity of 0.652 ± 0.006 eV and a singlet-triplet splitting of 9.7± 0.09 kcal/mol.Abstract:
Photoelectron spectra are reported for the CH2(X 3B1)+e−←CH−2 (X 2B1) and CH2(a 1A1)+e−←CH−2 (X 2B1) transitions of the methylene and perdeuterated methylene anions, using a new flowing afterglow photoelectron spectrometer with improved energy resolution (11 meV). Rotational relaxation of the ions to ∼300 K and partial vibrational relaxation to <1000 K in the flowing afterglow negative ion source reveal richly structured photoelectron spectra. Detailed rotational band contour analyses yield an electron affinity of 0.652±0.006 eV and a singlet–triplet splitting of 9.00±0.09 kcal/mol for CH2. (See also the following paper by Bunker and Sears.) For CD2, results give an electron affinity of 0.645±0.006 eV and a singlet–triplet splitting of 8.98±0.09 kcal/mol. Deuterium shifts suggest a zero point vibrational contribution of 0.27±0.40 kcal/mol to the observed singlet–triplet splitting, implying a Te value of 8.7±0.5 kcal/mol. Vibrational and partially resolved rotational structure is observed up to ∼9000 c...read more
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Atomic and molecular electron affinities: photoelectron experiments and theoretical computations.
Jonathan C. Rienstra-Kiracofe,Gregory S. Tschumper,Henry F. Schaefer,Sreela Nandi,G. Barney Ellison +4 more
TL;DR: Theoretical D determination of Electron Affinities and Statistical Analysis of DFT Results ThroughComparisons to Experiment and Other theoretical Methods and Specific Theoretical Successes 251E.
Journal ArticleDOI
The nature of the bonding in transition-metal compounds.
Journal ArticleDOI
A complete basis set model chemistry. IV. An improved atomic pair natural orbital method
TL;DR: An improved complete basis set-quadratic configuration interaction/atomic pair natural orbital (CBS•QCI/APNO) model is described in this paper, which provides chemical energy differences (i.e., D0 I.P., and E.A.) with a mean absolute error of 0.53 kcal/mol.
Journal ArticleDOI
A combination of kohn-sham density functional theory and multi-reference configuration interaction methods
Stefan Grimme,Mirko Waletzke +1 more
TL;DR: An effective Hamiltonian in a basis of spin and space-symmetry adapted configuration state functions (CSF), which includes information from Kohn-Sham density functional theory (DFT), is used to calculate configuration interaction (CI) wave functions for the electronic states of molecules as mentioned in this paper.
Journal ArticleDOI
Photoelectron spectroscopy of metal cluster anions : Cu−n, Ag−n, and Au−n
TL;DR: In this paper, negative ion photoelectron spectra of Cu−n, Ag−n(n=1-10), and Au−n (n= 1-5) are presented for electron binding energies up to 3.35 eV at an instrumental resolution of 6-9 meV.
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