Active Thermochemical Tables: Enthalpies of Formation of Bromo- and Iodo-Methanes, Ethenes and Ethynes.

The thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new Feller-Peterson-Dixon (FPD) style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the Active Thermochemical Tables (ATcT). From the computational viewpoint, a slower convergence of the components of composite thermochemistry methods is observed relative to species that solely contain first row elements, leading to a higher computational expense for achieving comparable levels of accuracy. Potential systematic sources of computational uncertainty are investigated, and, not surprisingly, spin-orbit coupling is found to be a critical component, particularly for iodine containing molecular species. The ATcT analysis of available experimental and theoretical determinations indicates that prior theoretical determinations have significantly larger uncertainties than originally reported, particularly in cases where molecular spin-orbit effects were ignored. Accurate and reliable heats of formation are reported for 38 halogen containing systems, based on combining the current computations with previous experimental and theoretical work via the ATcT approach.

Orbital contraction and covalent bonding.

According to Ruedenberg's classic treatise on the theory of chemical bonding [K. Ruedenberg, Rev. Mod. Phys. 34, 326-376 (1962)], orbital contraction is an integral consequence of covalent bonding. While the concept is clear, its quantification by quantum chemical calculations is not straightforward, except for the simplest of molecules, such as H2 + and H2. This paper proposes a new, yet simple, approach to the problem, utilizing the modified atomic orbital (MAO) method of Ehrhardt and Ahlrichs [Theor. Chim. Acta 68, 231 (1985)]. Through the use of MAOs, which are an atom-centered minimal basis formed from the molecular and atomic density operators, the wave functions of the species of interest are re-expanded, allowing the computation of the kinetic energy (and any other expectation value) of free and bonded fragments. Thus, it is possible to quantify the intra- and interfragment changes in kinetic energy, i.e., the effects of contraction. Computations are reported for a number of diatomic molecules H2, Li2, B2, C2, N2, O2, F2, CO, P2, and Cl2 and the polyatomics CH3-CH3, CH3-SiH3, CH3-OH, and C2H5-C2H5 (where the single bonds between the heavy atoms are studied) as well as dimers of He, Ne, Ar, and the archetypal ionic molecule NaCl. In all cases, it is found that the formation of a covalent bond is accompanied by an increase in the intra-fragment kinetic energy, an indication of orbital contraction and/or deformation.

The Basics of Covalent Bonding in Terms of Energy and Dynamics.

We address the paradoxical fact that the concept of a covalent bond, a cornerstone of chemistry which is well resolved computationally by the methods of quantum chemistry, is still the subject of debate, disagreement, and ignorance with respect to its physical origin. Our aim here is to unify two seemingly different explanations: one in terms of energy, the other dynamics. We summarize the mechanistic bonding models and the debate over the last 100 years, with specific applications to the simplest molecules: H2+ and H2. In particular, we focus on the bonding analysis of Hellmann (1933) that was brought into modern form by Ruedenberg (from 1962 on). We and many others have helped verify the validity of the Hellmann-Ruedenberg proposal that a decrease in kinetic energy associated with interatomic delocalization of electron motion is the key to covalent bonding but contrary views, confusion or lack of understanding still abound. In order to resolve this impasse we show that quantum mechanics affords us a complementary dynamical perspective on the bonding mechanism, which agrees with that of Hellmann and Ruedenberg, while providing a direct and unifying view of atomic reactivity, molecule formation and the basic role of the kinetic energy, as well as the important but secondary role of electrostatics, in covalent bonding.

The Virial Theorem and Covalent Bonding.

A long-held view of the origin of covalent binding is based on the notion that electrostatic forces determine the stability of a system of charged particles and that, therefore, potential energy changes drive the stabilization of molecules. A key argument advanced for this conjecture is the rigorous validity of the virial theorem. Rigorous in-depth analyses have however shown that the energy lowering of covalent bonding is due to the wave mechanical drive of electrons to lower their kinetic energy through expansion. Since the virial theorem applies only to systems with Coulombic interaction potentials, its relevance as a foundation of the electrostatic view is tested here by calculations on analogues of the molecules H2+ and H2, where all 1/ r interaction potentials are replaced by Gaussian-type potentials that yield one-electron "atoms" with realistic stability ranges. The virial theorem does not hold in these systems, but covalent bonds are found to form nonetheless, and the wave mechanical bonding analysis yields analogous results as in the case of the Coulombic potentials. Notably, the key driving feature is again the electron delocalization that lowers the interatomic kinetic energy component. A detailed discussion of the role of the virial theorem in the context of covalent binding is given.

Covalent Bonding in the Hydrogen Molecule.

This work addresses the continuing disagreement between two schools of thought concerning the mechanism of covalent bonding. According to Hellmann, Ruedenberg, and Kutzelnigg, covalent bonding is a quantum mechanical phenomenon whereby lowering of the kinetic energy associated with electron sharing, i.e., delocalization, is the key stabilization mechanism. The opposing view of Slater, Feynman, and Bader has maintained that the source of stabilization is electrostatic potential energy lowering due to electron density redistribution to binding regions between nuclei. Following our study of H2+ we present an analogous detailed study of H2 where bonding involves an electron pair with repulsion and correlation playing a significant role in its properties. We use a range of different computational approaches to study and reveal the relevant contributions to bonding as seen in the electron density and corresponding kinetic and potential energy distributions. The energetics associated with the more complex electronic structure of H2, when examined in detail, clearly agrees with the analysis of Ruedenberg; i.e., covalent bonding is due to a decrease in the interatomic kinetic energy resulting from electronic delocalization. Our results support the view that covalent bonding is a quantum dynamical phenomenon requiring a properly quantized kinetic energy to be used in its description.

Resonance-Enhanced 2-Photon Ionization Scheme for C2 through a Newly Identified Band System: 4(3)Πg-a(3)Πu.

We report the observation of a new band system of C2, namely, the 4(3)Πg-a(3)Πu system. The bands, observed by resonant 2-photon ionization spectroscopy and time-of-flight mass spectrometry, were identified through a synergy of high-level ab initio computation and double-resonance spectroscopy. Two bands are firmly identified, 1-3 and 0-2, allowing the 4(3)Πg origin to be placed at 51496.44 cm(-1). The 4(3)Πg state is characterized as having a single bond, with a vibrational frequency of about 1268 cm(-1), and an equilibrium bond length of 1.57 Å. The state is predicted to exhibit a barrier to dissociation, with a rotational constant that unusually increases with vibrational excitation up to a maximum before decreasing at higher vibrational excitation. The new band system allows us to probe the a(3)Πu state of C2 through a straightforward 1 + 1 REMPI scheme.

NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively.

Excitation spectra of large jet-cooled polycyclic aromatic hydrocarbon radicals: 9-anthracenylmethyl (C15H11) and 1-pyrenylmethyl (C17H11).

The 9-anthracenylmethyl (C15H11) and 1-pyrenylmethyl (C17H11) radicals were identified by a combination of mass-resolved laser spectroscopy of a jet-cooled electrical discharge and quantum chemical methods. The 9-anthracenylmethyl radical was found to exhibit an origin band at 13757 cm(-1), with vibrational structure observed in a1 modes, and even quanta of b1 and a2 modes. The 1-pyrenylmethyl radical was found to exhibit an origin band at 13,417 cm(-1), with a more complex vibrational structure as compared to 9-anthracenylmethyl, on account of its lower symmetry and larger size. The origin bands of these species were predicted to within 250 cm(-1) by fitting a linear relationship between observed origin wavelengths of similar chromophores and the calculated TD-B3LYP transition energies. A refined fit including the title radicals provides estimated absorption energies for the larger 2-perylenylmethyl and 6-anthanthrenylmethyl species of 1.44 and 1.41 eV, respectively, with an estimated error of 30 meV.

Covalent bonding: the fundamental role of the kinetic energy.

This work addresses the continuing disagreement between two prevalent schools of thought concerning the mechanism of covalent bonding. According to Hellmann, Ruedenberg, and Kutzelnigg, a lowering of the kinetic energy associated with electron delocalization is the key stabilization mechanism. The opposing view of Slater, Feynman, and Bader has maintained that the source of stabilization is electrostatic potential energy lowering due to electron density redistribution to binding regions between nuclei. Despite the large body of accurate quantum chemical work on a range of molecules, the debate concerning the origin of bonding continues unabated, even for H2(+), the simplest of covalently bound molecules. We therefore present here a detailed study of H2(+), including its formation, that uses a sequence of computational methods designed to reveal the relevant contributing mechanisms as well as the spatial density distributions of the kinetic and potential energy contributions. We find that the electrostatic mechanism fails to provide real insight or explanation of bonding, while the kinetic energy mechanism is sound and accurate but complex or even paradoxical to those preferring the apparent simplicity of the electrostatic model. We further argue that the underlying mechanism of bonding is in fact of dynamical character, and analyses that focus on energy do not reveal the origin of covalent bonding in full clarity.

Excitation spectra of the jet-cooled 4-phenylbenzyl and 4-(4'-methylphenyl)benzyl radicals.

The excitation spectra of jet-cooled 4-phenylbenzyl and 4-(4'-methylphenyl)benzyl radicals have been identified by a combination of resonant two-color two-photon ionization mass spectrometry and quantum chemical methods. Both radicals exhibit progressions in the biphenyl torsional mode, peaking near ν = 17. The lowest observed peak for 4-phenylbenzyl was observed at 18598 cm(-1) and is estimated to be the ν = 3 of the progression, while the lowest observed peak for the 4-(4'-methylphenyl)benzyl radical was observed at 18183 cm(-1) and is possibly the origin. The spectra are discussed and compared to other biphenyl and benzyl chromophores.

Spectroscopy and dynamics of the predissociated, quasi-linear S2 state of chlorocarbene.

In this work, we report on the spectroscopy and dynamics of the quasi-linear S(2) state of chlorocarbene, CHCl, and its deuterated isotopologue using optical-optical double resonance (OODR) spectroscopy through selected rovibronic levels of the S(1) state. This study, which represents the first observation of the S(2) state in CHCl, builds upon our recent examination of the corresponding state in CHF, where pronounced mode specificity was observed in the dynamics, with predissociation rates larger for levels containing bending excitation. In the present work, a total of 14 S(2) state vibrational levels with angular momentum l = 1 were observed for CHCl, and 34 levels for CDCl. The range of l in this case was restricted by the pronounced Renner-Teller effect in the low-lying S(1) levels, which severely reduces the fluorescence lifetime for levels with K(a) > 0. Nonetheless, by exploiting different intermediate S(1) levels, we observed progressions involving all three fundamental vibrations. For levels with long predissociation lifetimes, rotational constants were determined by measuring spectra through different intermediate J levels of the S(1) state. Plots of the predissociation linewidth (lifetime) vs. energy for various S(2) levels show an abrupt onset, which lies near the calculated threshold for elimination to form C((3)P) + HCl on the triplet surface. Our experimental results are compared with a series of high level ab initio calculations, which included the use of a dynamically weighted full-valence CASSCF procedure, focusing maximum weight on the state of interest (the singlet and triplet states were computed separately). This was used as the reference for subsequent Davidson-corrected MRCI(+Q) calculations. These calculations reveal the presence of multiple conical intersections in the singlet manifold.

Spectroscopy and thermochemistry of a jet-cooled open-shell polyene: 1,4-pentadienyl radical.

The 1,4-pentadienyl (vinylallyl) radical has been observed for the first time by optical spectroscopy. An excitation spectrum is recorded on m/z 67 by resonant two-color two-photon ionization spectroscopy. Several bands are observed with the origin transition identified at 19 449 cm(-1). The spectrum is assigned by a comparison with ab initio frequencies calculated at the CASPT2/cc-pVTZ level of theory, with an accompanying Franck-Condon calculation of the excitation spectrum, including Dushinsky mixing. The b(1) and a(2) outer C-C bond torsional modes are calculated to halve in frequency upon electronic excitation, bringing about their appearance in the excitation spectrum. This can be readily understood by considering the torsional sensitivity of the frontier molecular orbital energies. High-level quantum chemical calculations of the radical stabilization energy, resulting in a value of nearly 120 kJ mol(-1), provide quantitative confirmation that this radical is highly stabilized.

Hydrogen abstraction by chlorine atom from amino acids: remarkable influence of polar effects on regioselectivity.

Quantum chemistry computations have been used to investigate hydrogen-atom abstraction by chlorine atom from protonated and N-acetylated amino acids. The results are consistent with the decreased reactivity at the backbone α-carbon and adjacent side-chain positions that is observed experimentally. The individual effects of NH(3)(+), COOH, and NHAc substituents have been examined and reveal important insights. The NH(3)(+) group in isolation is found to be deactivating at the α-position, while the acetamido group is activating. For the COOH group, polar effects lead to a contrathermodynamic deactivation of the thermodynamically most favorable α-abstraction. In the N-acetylamino acid, the α-position is deactivated by the combined inductive effect of the substituents and the presence of an early transition structure, again overriding the greater thermodynamic stability of the α-centered radical product. Deactivation of the α-, ß-, and γ-positions results in a peculiar stability for amino acids and peptides and their derivatives with respect to radical degradation.

The 1(5)Π(g) state of C2.

We report ab initio spectroscopic constants for the recently identified 1(5)Π(g) state of C(2) [P. Bornhauser, Y. Sych, G. Knopp, T. Gerber, and P. P. Radi, J. Chem. Phys. 134, 044302 (2011)]. The calculations are performed at the multi-reference configuration interaction level of theory with Davidson's correction using aug-cc-pV6Z basis sets and include core-valence correlation and relativistic corrections obtained with quadruple-zeta bases. Such treatment accurately reproduces the experimentally observed constants of the a(3)Π(u) and other states. Thus, we expect our calculated ω(e) value for the 1(5)Π(g) state to be within a few cm(-1), and rotational constants to be within 0.1% of experiment. Agreement with available spectroscopic data is excellent, with the calculations strongly suggesting that the 1(5)Π(g) vibrational level observed by Bornhauser et al. is v = 0.

Quantum chemical characterization of the X((1)A'), a((3)A'') and A((1)A'') states of CHBr and CHI and computed heats of formation for CHI and CI.

The relative energies of the X, a, and A states of CHBr and CHI and their atomization and dissociation energies in the complete basis limit were determined by extrapolating (R/U)CCSD(T) and Davidson corrected MRCI energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets, which were corrected for core-valence correlation, spin-orbit coupling, and zero point energies. The all-electron calculations on the bromine containing molecules were explicitly corrected for scalar relativity, while in the iodo systems they are implicit in the ECP28MDF pseudopotential of iodine. The geometries and vibrational frequencies were calculated at the CASPT2/cc-pVTZ level of theory. The computed singlet-triplet splittings (5.7 and 3.7 kcal mol(-1) for CHBr and CHI respectively) are in close agreement with the recent experimental values, while the predicted A <-- X excitation energies are within approximately 1 kcal mol(-1) of experiment. The barriers to linearity and dissociation on the A surface were also characterized. For CHI and CI, the predicted heats of formation at 298 K are 134.5 +/- 1.0 and 103.9 +/- 1.0 kcal mol(-1), respectively. The spin-orbit splitting in iodomethylidyne (CI) is computed to be 746 cm(-1), although that value may be an underestimate by approximately 20%.

Quantum chemical study and experimental observation of a new band system of C(2), e 3Pi(g)-c 3Sigma(u)+.

A new band system of C(2), e (3)Pi(g)-c (3)Sigma(u)(+) was studied by ab initio quantum chemical and experimental methods. The calculations were carried out at the multireference configuration interaction level of theory with Davidson's correction using aug-cc-pV6Z basis set and include core and core-valence correlation as well as relativistic corrections computed with aug-cc-pCVQZ and cc-pVQZ bases, respectively. The vibrational energies and rotational constants of the upper e (3)Pi(g) state were calculated from the computed ab initio potential energy curve. The ab initio results indicate that the electronic transition moment of the e (3)Pi(g)-c (3)Sigma(u)(+) system is approximately one-half that of the Fox-Herzberg e (3)Pi(g)-a (3)Pi(u) system. Franck-Condon factors were calculated for both systems and used to guide experiments aimed at discovering the e (3)Pi(g)-c (3)Sigma(u)(+) system. The e (3)Pi(g)(v(') = 4)-c (3)Sigma(u)(+)(v(") = 3) band of jet-cooled C(2) was successfully observed by laser-induced fluorescence spectroscopy by monitoring the ensuing e (3)Pi(g)-a (3)Pi(u) emission.

Hydrogen abstraction by chlorine atom from small organic molecules containing amino acid functionalities: an assessment of theoretical procedures.

A high-level quantum chemistry investigation has been carried out for the abstraction by chlorine atom of hydrogen from methane and five monosubstituted methanes, chosen to reflect the chemical functionalities contained in amino acids and peptides. A modified W1' procedure is used to calculate benchmark barriers and reaction energies for the six reactions. The reactions demonstrate a broad range of barrier heights and reaction energies, which can be rationalized using curve-crossing and molecular orbital theory models. In addition, the performance of a range of computationally less demanding electronic structure methods is assessed for calculating the energy profiles for the six reactions. It is found that the G3X(MP2)-RAD procedure compares best with the W1' benchmark, demonstrating a mean absolute deviation (MAD) from W1' of 2.1 kJ mol(-1). The more economical RMP2/G3XLarge and UB2-PLYP/G3XLarge methods are also shown to perform well, with MADs from W1' of 2.9 and 3.0 kJ mol(-1), respectively.

The Sharpless asymmetric aminohydroxylation reaction: optimising ligand/substrate control of regioselectivity for the synthesis of 3- and 4-aminosugars.

An investigation of the factors responsible for the sense and magnitude of regioselectivity in the Sharpless asymmetric aminohydroxylation (AA) has been conducted. Theoretical investigations of ligand-osmium binding geometry and experimental investigations of the Sharpless AA reaction on a series of functionalized pent-2-enoic acid ester substrates demonstrate that the opposite regioselectivity afforded using PHAL and AQN ligands results from a change in substrate orientation with respect to the catalyst. Two distinct ligand binding domains within the catalyst have been proposed that undergo attractive interactions with the substrates. Selective access to each of the four potential regio- and stereo-isomeric AA products could be achieved through the appropriate choice of ligand and substrate. These results have been applied toward the efficient stereoselective synthesis of naturally occurring and regioisomeric 3- and 4-aminosugar derivatives.

Oscillator strengths of the Mulliken, Swan, Ballik-Ramsay, Phillips, and d3Pi g<--c 3Sigma u+ systems of C2 calculated by MRCI methods utilizing a biorthogonal transformation of CASSCF orbitals.

Ab initio oscillator strengths and lifetimes for the D (1)Sigma(u) (+)<--X (1)Sigma(g) (+) Mulliken system of C(2) are reported. The calculations were carried out at the MRCI level of theory with Davidson's correction using aug-cc-pV6Z basis sets and include core and core-valence correlation as well as relativistic corrections, computed with aug-cc-pCVQZ and cc-pVQZ bases, respectively. The MRCI calculations of transition moments utilize a biorthogonal transformation of the CASSCF orbitals. This approach was also employed to recompute the transition moments of the Swan, Ballik-Ramsay, Phillips, and d (3)Pi(g)<--c (3)Sigma(u) (+) systems of C(2), which were the subject of our previous study [D. L. Kokkin et al., J. Chem. Phys. 126, 084302 (2007)], resulting in an improved set of oscillator strengths for the latter systems as well. The oscillator strength of the Mulliken origin band, f(00) (DA), was calculated to be 0.0535, in excellent agreement with the accepted astronomical value of 0.054.

Oscillator strengths and radiative lifetimes for C2: Swan, Ballik-Ramsay, Phillips, and d 3Pig<--c 3Sigmau+ systems.

High level ab initio calculations, using multireference configuration interaction (MRCI) techniques, have been carried out to investigate the spectroscopic properties of the singlet A 1Piu<--X 1Sigmag+ Phillips, the triplet d 3Pig<--a 3Sigmau Swan, the b 3Sigmag-<--a 3Piu Ballik-Ramsay, and the d 3Pig<--c 3Sigmau+ transitions of C2. The MRCI expansions are based on full-valence complete active space self-consistent-field reference states and utilize the aug-cc-pV6Z basis set to resolve valence electron correlation. Core and core-valence correlations and scalar relativistic energy corrections were also incorporated in the computed potential energy surfaces. Nonadiabatic and spin-orbit effects were explored and found to be of negligible importance in the calculations. Harmonic frequencies and rotational constants are typically within 0.1% of experiment. The calculated radiative lifetimes compare very well with the available experimental data. Oscillator strengths are reported for all systems: fv'v", where 0