𝔖 Bobbio Scriptorium
✦   LIBER   ✦

A successful ab initio study of the adiabatic electron affinity of the methyl radical

✍ Scribed by Ulrike Salzner; Paul von Ragué Schleyer

Publisher
Elsevier Science
Year
1992
Tongue
English
Weight
726 KB
Volume
199
Category
Article
ISSN
0009-2614

No coin nor oath required. For personal study only.

✦ Synopsis

A stable methyl anion, i.e. a positive adiabatic electron atlinity for the methyl radical, has been calculated directly by ab initio methods for the first time. The basii set was uncontmeted in the valence region and augmented by four d and two f timctions on carbon and three p and one d sets on hydrogen. At the CCD+ST(CCD) level the electron affiity is 0.23 kcal/mol or 0.010 eV. Tbe CCD+ST(CCD) and QCISD(T) results are nearly identical for all basis sets considered. Zero-point energy corrections are estimated to contribute 0.034 eV. Thus, the calculated EA is nearly within the experimental error bound of 0.08 + 0.03 eV. The computed equilibrium geometry of CH,-is pyramidal also at a MPZ/large basis set level where the anion is bound. The wavefunction is well represented by a single determinant (the co&cient of the dominant configuration in the CCD+ ST( CCD) expansion bemg 0.976, the next largest coefficient 0.039). The MW and even the MP2 values are surprisingly close to the CCDtST(CCD) and QCISD(T) results.

📜 SIMILAR VOLUMES

An ab initio study of the electron affin
An ab initio study of the electron affinity of O2
✍ Remedios González-Luque; Manuela Merchán; Markus P. Fülscher; Björn O. Roos 📂 Article 📅 1993 🏛 Elsevier Science 🌐 English ⚖ 902 KB

Coupled pair functional, multiconfigurational second-order perturbation theory, and multireference CI methods have been applied in a calculation of the electron affinity of the oxygen molecule. The convergence of the theoretical result has been checked with respect to a systematic expansion of the o

Ab initio study of the electronic spectr
Ab initio study of the electronic spectrum of the PO2 radical
✍ Z.-L. Cai; Gerhard Hirsch; Robert J. Buenker 📂 Article 📅 1996 🏛 Elsevier Science 🌐 English ⚖ 479 KB

Ab initio electronic structure calculations are reported for 18 electronic states of the PO 2 radical. Geometric parameters for the X 2A x ground state are calculated at the MRD-CI level with a triple-zeta basis set plus two polarization d functions, as well as Rydberg functions. The vertical excita

Theoretical ab initio calculations of th
Theoretical ab initio calculations of the electron affinity of thymine
✍ Nathan A. Oyler; Ludwik Adamowicz 📂 Article 📅 1994 🏛 Elsevier Science 🌐 English ⚖ 452 KB

It was determined in ab initio calculations that an electron can attach to thymine, forming a stable anion. The electron is attached predominantly to the positive end of the molecular dipole moment; however, some contribution from the covalent character is also present. The adiabatic electron affini

Ab initio study of the outer valence ion
Ab initio study of the outer valence ionization potentials and electron affinities of benzocycloalkenes
✍ V. Galasso 📂 Article 📅 1990 🏛 Elsevier Science 🌐 English ⚖ 276 KB

Ab initio many-body calculations according to Cederbaum's outer-valence Green-function formalism have been carried out on the ionization potentials of bicyclo[4.l.O]hepta-1,3,5-triene, bicycIo[ 4.2.0]octa-1,3,5-triene, tricyclo[ 5.1.0.03,5]octa-1,3(5),6triene, tricyclo[ 6.2.0.03,6]deca-1,3(6),7-trie

A photoelectron and ab initio study of t
A photoelectron and ab initio study of the CH3SCH2 radical
✍ J. Baker; J.M. Dyke 📂 Article 📅 1993 🏛 Elsevier Science 🌐 English ⚖ 398 KB

A new partially structured photoelectron band appearing early in the F+CH,SCH, reaction has been assigned to the primary reaction product, CHpSCH2. This band, with adiabatic and vertical ionisation energies of 6.85 kO.03 and 7.16+0.03 eV, respectively, shows structure in two vibrational modes, with