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Professor, Physical Chemistry
B.S. 1982, Bradley University
Ph.D. 1987, University of Wisconsin, Madison
Postdoctoral: 1988-1989, Northeastern University
1990, University of Oregon
Email: standard@ilstu.edu
Phone: (309)438-7700
Office: 222A Julian Hall
Research in my group
is in the area of computational chemistry. The major themes of my
research include the study of weakly bound systems, such as van
der Waals molecules and hydrogen-bonded complexes; investigations
of the dynamics of wide-amplitude and highly-excited molecular
vibrations; probing of photodissociation and other decay processes
in small molecules; and the investigation of metastable states of
atoms and molecules. Understanding vibrational dynamics and
photodissociation processes requires a knowledge of potential
energy surfaces for the molecular system of interest; therefore,
we also are engaged in developing methods for determining
potential energy surfaces for small molecules and complexes.
Students in the group generally
will be involved in running several different simulation and
computer graphics programs on Unix workstations. Techniques
employed include a variety of quantum and classical mechanics
methods. Though computer programming experience is not required
to work in the group, students with programming experience may
also be involved in developing computer programs. Listed below
are a few current projects.
The Formation of Acid Rain in the Atmosphere
Sulfur emissions into the earth's atmosphere consist primarily
of sulfur dioxide, SO2, from fossil fuel combustion.
Sulfur dioxide is oxidized to sulfur trioxide, which is then
converted into sulfuric acid, H2SO4, one of
the principal components of acid rain. One set of steps in the
mechanism involves oxidation of sulfur dioxide to sulfur trioxide,
SO3. Sulfur trioxide then reacts with water to form an
intermediate molecular complex, SO3–H2O. The
molecular complex rearranges to form sulfuric acid, H2SO4.
It is believed that the activation energy required for conversion
of the intermediate complex to acid rain is reduced significantly
by the presence of additional water molecules. We are
investigating the effects that additional water molecules have on
the structure and energetics of acid rain precursors using a
variety of quantum mechanical methods.
The SO3–H2O complex
Interactions of Singlet Carbenes with Heteroatom-containing Compounds
For the past few years, my research group has been involved in
carrying out computational studies of singlet carbenes and
intermolecular complexes formed from singlet carbenes, such as
ylides. Ylides are formed from the interaction of molecules
containing a heteroatom (such as N, P, O, S, F, or Cl) with a
singlet carbene molecule. Such intermolecular complexes are
often difficult to study experimentally, due to their short
lifetimes and high reactivity.
The H2S-CH2 ylide.
Sulfur ylides are formed when a
molecule containing a sulfur atom interacts with a singlet
carbene. The lone pair electrons on the sulfur interact with an
empty orbital on the carbene. Sulfur ylides are important
symthetic intermediates which have recently been employed in the
production of designer polymers and the formation of metal-carbene
complexes. High-level, large-scale computational studies of
sulfur ylides are being performed in order to investigate their
structures, properties, energetics, and bonding.
Computational Studies of Alkanethiols Chemisorbed on Noble Metal Surfaces
Alkanethiols chemisorbed on noble metal surfaces form
self-assembled monolayers (SAMs), which consist of densely
packed hydrocarbon chains bound to the surface through a
covalent interaction between sulfur headgroup and metal surface.
Experimental observations of surface-enhanced electronic Raman
scattering (SEERS) have been made for alkanethiol SAMs on
roughened silver and gold surfaces. In conjunction with
Professors Brian Clark and Brian Gregory, we have shown that the
electrons involved in SEERS are located in the vicinity of the
sulfur headgroup region. Therefore, the electronic structure of
the headgroup region plays a key role in understanding the
energetics of the alkanethiol SAM systems.
Because the recent modeling studies suggest that the electron is
localized in the headgroup region, the electronic structure and
bonding of the sulfur interacting with the metal surface must be
elucidated. In this project, ab initio quantum mechanical
calculations are being carried out to obtain a wealth of
information about the electronic structure of the system. The
focus of the project is two-fold: first, high-level studies are
being completed to investigate the interactions of thiolate (and
selenate) species with small gold and silver clusters; second,
electronic structure calculations are being performed to determine
the interactions of two or more thiolate species on larger gold
and silver clusters.
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SELECTED PUBLICATIONS
J. M. Standard, B. W. Gregory, and B. K. Clark, "Computational Studies of Copper, Silver, and Gold Alkanethiolates and Alkaneselenates," Theochem 803 (2007) 103-113.
B. N. Ida, P. S. Fudacz, D. H. Pulsifer, and J. M. Standard, "A Gas- and Condensed-Phase Density Functional Study of Donor-Acceptor Complexes of Sulfur Trioxide," J. Phys. Chem. A 110 (2006) 5831-5838.
E. W. Olson and J. M. Standard, "Structure and Bonding in Hexamethyldisilazane and a Series of Analogues, (XH3)2YH (X=C, Si, Ge and Y=N, P, As), by Ab Initio and Density Functional Methods," Theochem 719 (2005) 17-30.
J. Goodwin, T. Kurtikyan, B. Zheng, D. Parmley, J. Howard, S. Green, R. Walsh, J. Standard, D. Przybyla, and A. Mardyukov, "Variation of Oxo-transfer Reactivity of (Nitro) Cobalt Picket Fence Porphyrin with Distal Oxygen-Donating Ligands," Inor. Chem. 44 (2005) 2215-2223.
M. D. Squire, R. A. Davis, K. A. Chianakas, G. M. Ferrence, J. M. Standard, and S. R. Hitchcock, "Synthesis, X-ray crystallography, and computational studies concerning an oxadiazinone derived from D-camphor. Structural limitations of oxadiazinones as chiral auxiliaries," Tetrahedron: Asymmetry 16 (2005) 1047-1053.
J. M. Standard, I. S. Buckner, and D. H. Pulsifer, "Basis Set Effects in Ab Initio Studies of Sulfur Trioxide-Water Complexes," Theochem 673 (2004) 1-16.
J. R. Burgeson, M. Renner, I. Hardt, G. M. Ferrence, J. M. Standard, and S. R. Hitchcock, "Towards the Development of a Structurally Novel Class of Chiral Auxiliaries. Conformational Properties of the Aldol Adducts of Oxadiazinones: Observation of Unusual Shielding Effects," J. Org. Chem. 69 (2004) 727-734.
P. S. Fudacz, J. D. Dober, D. L. Jarman, J. M. Standard, and R. W. Quandt, "An Ab Initio Investigation of the Ground and First Two Excited States of the Difluoromethyl Radical," J. Phys. Chem. A, 107 (2003) 9730-9735.
J. M. Standard and R. W. Quandt, "A CASPT2 Investigation of the Ground and First Excited Electronic States of Fluoroiodocarbene," J. Phys. Chem. A 107 (2003) 6877-6881.
D. M. Casper, J. R. Blackburn, C. D. Maroules, T. Brady, J. M. Esken, G. M. Ferrence, J. M. Standard, and S. R. Hitchcock, "Conformational Studies of N3-Substituted [1,3,4]-Oxadiazinan-2-ones," J. Org. Chem. 67 (2002) 8871-8876.
A. Avila, B. W. Gregory, B. K. Clark, J. M. Standard, and T. M. Cotton, "Image Potential Surface States Localized at Chemisorped Dielectric-Metal Interfaces," Langmuir 18 (2002) 4709-4719.
S. A. Drake, J. M. Standard, and R. W. Quandt, "An Ab Initio Investigation of the Ground and Excited Electronic State Properties of Bromine- and Iodine-Containing Singlet Carbenes," J. Phys. Chem. A 106 (2002) 1357-1364.
Complete List
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