Accurate Theoretical Determination of Molecular
Properties
Members:
- Dr. Manuela.Merchan
- Dr. Remedios González-Luque
- Dr. Luis Serrano-Andrés
- Dr. Rosendo Pou-Amérigo
- Dr. Mercedes Rubio
- Mr. Vicent Molina
Research Activities
The work interest in this line is focused on the accurate
determination of molecular properties of chemical compounds.
Highly correlated ab initio quantum chemical methods are
employed for this purpose. The major effort has been devoted
on studies of electronic spectroscopy of organic compounds
of current chemical and biological relevance. These studies
comprise:
- Calculation of radiative lifetimes
(A3P
state of OH+ and SH+)
- Determination of electron affinities (NH2,
O2, O3, NO2,
SO2, ...).
- Ionization energies (NO, NO2, ....).
- Barriers for chemical reactions (e.g., the
F + H2 = HF + H reaction).
- Weak intermolecular interactions: determination of the
dissociation energy of the nitric oxide dimer (the
cis-N2O2 molecule).
- Transition metal chemistry:
- Construction of basis sets based on Atomic Natural
Orbitals (ANO).
- Characterization of the bonding in CuH, Cu2,
NiH, and Ni2.
- Polyenes and polyenals: butadiene, hexatriene,
octatetraene, retinal, undecapentaenal, and a protonated
Schiff base.
- Heterocycles: cyclopentadiene, furan, pyrrole, thiophene,
norbornadiene.
- Three-membered rings: cyclopropene, methylenecyclopropene,
doxirane, dioxymethane and its anion.
- Alternant and nonalternant hydrocarbons and their cations:
naphthalene, biphenyl, stilbene, biphenylene, azulene,
fluoranthene, benzofuran, acenaphthylene, dibenzofuran,
and dibenzothiophene.
- Oligomers of thiophene: bithiophene, terthiophene.
- TICT process: aminobenzonitriles and N-phenylpyrroles.
- Protein chromophores: imidazole, indole, peptides,
polypeptides, amino acids.
- Nucleic acid monomers and related compounds: adenine,
guanine, purine.
- Carbonyl group: formaldehyde and acetone.
- Radical cations: cumene, phenylcyclopropane, toluene,
benzene.
- Porphirins: free base porphin and related systems.
- Dyes: indigo and indigoid dyes.
Collaborations
Part of the work has been performed in collaboration with:
- Prof. B. O. Roos and members of his group of the Department
of Theoretical Chemistry, Lund University, Sweden.
- Dr. E. Ortí of the Departamento de Química
Física, Universitat de València, Spain.
Sponsors
The research is currently supported by:
- DGICYT of the Ministerio de Educación y
Cultura of Spain through the project number
PB94-0986.
- European Comission through the TMR network contract
ERB FMRX-CT96-0079, Quantum Chemistry of the Excited State,
QUCEX.
Postdoctoral positions
Postdoctoral openning positions within the TMR network
are available for work related to the above topics.
Applicants MUST be members of the European Union and not from Spain.
Interested applicants should send their CV, publication
lists, and letter of recommendation to
Manuela Merchán
Departamento de Química Física
Universitat de València
Dr. Moliner 50, Burjassot
E-46100 Valencia, Spain
or send via e-mail to
Manuela.Merchan@uv.es
General information about the network can be obtained in
the QUCEX Webpage.
Selected Recent Publications
- B.O. Roos, M. Fülscher, P.-Å. Malmqvist, M.
Merchán and L. Serrano-Andrés
Theoretical studies of the electronic spectra of organic
molecules
in: Quantum mechanical electronic structure calculations
with chemical accuracy
Ed. S.R. Langhoff, Kluwer, Dordrecht, 357-438 (1995).
- B.O. Roos, K. Andersson, M.P. Fülscher, P.-Å.
Malmqvist, L. Serrano-Andrés, K. Pierloot and
M. Merchán
Multiconfigurational perturbation theory - applications
in electronic spectroscopy
in: Advances in Chemical Physics: New Methods in
Computational Quantum Mechanics. Eds. I. Prigogine
and S.A. Rice, John Wiley & Sons, New York,
Vol. 93, 219-331 (1996).
- M. Rubio, M. Merchán and E. Ortí
The internal rotational barrier of biphenyl studied with
multiconfigurational second-order perturbation theory
(CASPT2)
Theor. Chim. Acta, 91, 17-29 (1995).
- M. Merchán, R. Pou-Amérigo and B.O. Roos
A theoretical study of the dissociation energy of
Ni2+ - a case of broken symmetry
Chem. Phys. Lett., 252, 405-414 (1996).
- M. Rubio, M. Merchán, E. Ortí and B.O. Roos
A theoretical study of the electronic spectrum of
terthiophene
Chem. Phys. Lett., 248, 321-328 (1996).
- L. Serrano-Andrés and B. O. Roos
Theoretical study of the absorption and emission spectra
of indole in the gas phase and in solvents
J. Am. Chem. Soc., 118, 185-195 (1996)
- L. Serrano-Andrés and M. P.Fülscher
Theoretical study of the electronic spectroscopy of
peptides. I. The peptidic bond: primary, secondary,
and tertiary amines
J. Am. Chem. Soc., 118, 12190-12200 (1996).
- M. Merchán and R. González-Luque
Ab initio study on the low-lying excited states of retinal
J. Chem. Phys., 106, 1112-1122 (1997).
- V. Molina, M. Merchán and B.O. Roos
A theoretical study of the electronic spectrum of
trans-stilbene
J. Phys. Chem., 101, 3478-3487 (1997).
- L. Eberson, R. González-Luque, M. Merchán,
F. Radner, B.O. Roos and S. Shaik
Radical cations of non-alternant systems as probes of
the Shaik-Pross VB configuration mixing model
J. Chem. Soc., Perkin Trans. 2, 463-472 (1997).