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The reaction, BrO + HO2 → HOBr + O2, is exothermic and can produce O2 in both its ground state (X[combining tilde]3∑g-) and its first excited state (ã1Δg). As a result, this reaction can proceed on both a singlet and a triplet potential energy surface. Recently, Tsona, Tang and Du published a paper entitled "Impact of water on the BrO + HO2 gas-phase reaction: mechanism, kinetics and products (Phys. Chem. Chem. Phys. 2019, 21, 20296-203072). The results of this work showed significant differences from those published earlier on this reaction by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569). Further calculations performed in this present work, combined with higher level calculations published by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569), demonstrate that the work of Tsona et al. is flawed because the integration grid size used in their lowest singlet and triplet calculations is too small, and a closed-shell wavefunction, rather than an open-shell wavefunction, has been used for the singlet surface. The major conclusion in the work of Tsona et al. that the lowest singlet and triplet channels are barrierless is shown to be incorrect. Also, the computed rate coefficients of Tsona et al. showed a positive temperature dependence, which is inconsistent with the experimentally observed negative temperature dependence, whereas the singlet rate coefficients computed by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569) showed a negative temperature dependence consistent with experiment.

The reaction of hydroxymethyl hydroperoxide (HMHP, HOCH 2 OOH) with the simplest Criegee intermediate, CH 2 OO, has been examined using quantum chemical methods with transition state theory. Geometry optimization and IRC calculations were performed using the M06-2X, MN15-L, and B2PLYP-D3 functionals in conjunction with the aug-cc-pVTZ basis set. Single point energy calculations using QCISD(T) and BD(T) with the same basis set have been performed to determine the energy of reactants, reactive complexes, transition states, and products. Rate coefficients have been obtained using variational transition state theory. The addition of CH 2 OO on the three different oxygen atoms in HMHP has been considered and the ether oxide forming channel, CH 2 OO + HOCH 2 OOH → HOCH 2 O(O)CH 2 OOH (channel 2), is the most favorable. The best computed standard enthalpy of reaction (ΔH) and zero-point corrected barrier height are -20.02 and -6.33 kcal mol -1 , respectively. The reaction barrier is negative and our results suggest that both the inner and outer transition states contribute to the corresponding overall reactive flux in the tropospheric temperature range (220 K to 320 K). A two-transition state model has been used to obtain reliable rate coefficients at the high-pressure limit. The pressure-dependent rate coefficient calculations using the SS-QRRK theory have shown that this channel is pressure-dependent. Moreover, our investigation has shown that the ether oxide formed may rapidly react with SO 2 at 298 K to form SO 3 , which can, in turn, react with water to form atmospheric H 2 SO 4 . A similar calculation has been conducted for the reaction of HMHP with OH, suggesting that the titled reaction may be a significant sink of HMHP. Therefore, the reaction between CH 2 OO and HOCH 2 OOH could be an indirect source for generating atmospheric H 2 SO 4 , which is crucial to the formation of clouds, and it might relieve global warming.

A theoretical study has been made of the BrO + HO 2 reaction, a radical-radical reaction which contributes to ozone depletion in the atmosphere via production of HOBr. Reaction enthalpies, activation energies and mechanisms have been determined for five reaction channels. Also rate coefficients have been calculated, in the atmospherically important temperature range 200-400 K, for the two channels with the lowest activation energies, both of which produce HOBr: (R1a) HOBr(X 1 A') + O 2 (X 3 Σ) and (R1b) HOBr(X 1 A') + O 2 (a 1 Δ g ). The other channels considered are: (R2) BrO + HO 2 → HBr + O 3 , (R3) BrO + HO 2 → OBrO + OH and (R4) BrO + HO 2 → BrOO + OH. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/AVDZ level, while relative energies of the stationary points on the reaction surface were improved at a higher level (BD(TQ)/CBS or CCSD(T)/CBS). The computed standard reaction enthalpies (ΔH) for channels (R1a), (R1b), (R2), (R3) and (R4) are -47.5, -25.0, -4.3, 14.9 and 5.9 kcal mol -1 , and the corresponding computed activation energies (ΔE) are 2.53, -3.07, 11.83, 35.0 and 37.81 kcal mol -1 . These values differ significantly from those obtained in earlier work by Kaltsoyannis and Rowley (Phys. Chem. Chem. Phys., 2002, 4, 419-427), particularly for channel (R1b), and reasons for this are discussed. In particular, the importance of obtaining an open-shell singlet wavefunction, rather than a closed-shell singlet wavefunction, for the transition state of this channel is emphasized. Rate coefficient calculations from computed potential energy surfaces were made for BrO + HO 2 for the first time. Although channel (R1a) is the most exothermic, channel (R1b) has the lowest barrier height, which is negative (at -3.07 kcal mol -1 ). Most rate coefficient calculations were therefore made for (R1b). A two transition state model has been used, involving an outer and an inner transition state. The inner transition state was found to be the major bottleneck of the reaction with the outer transition state having essentially no effect on the overall rate coefficient (k) in the temperature range considered. Studying the entropy, enthalpy and free energy of activation of this channel as a function of temperature shows that the main contributor to the magnitude of ln k at a selected temperature is the entropy term (ΔS # /k B ) whereas the temperature dependence of ln k is determined mainly by the enthalpy term (-ΔH # /k B T). This compares with reactions with positive barrier heights where the enthalpy term makes a bigger contribution to ln k. Comparison of the computed rate coefficients with available experimental values shows that the computed values have a negative temperature dependence, as observed experimentally, but are too low by approximately an order of magnitude at any selected temperature in the range 200-400 K.

The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsX(n) molecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (ΔH(f)(Ø)). The recommended ΔH(f)(Ø) values obtained from the present investigation are AsH, 57.7(2); AsF, -7.9(3); AsCl, 27.2(4); AsH(2), 39.8(4); AsF(2), -96.6(9); AsCl(2), -17.8(10); AsH(3), 17.1(4); AsF(3)-196.0(5) and AsCl(3), -59.1(27) kcal mole(-1). These values are anchored only on one thermodynamic quantity, namely, ΔH(f)(Ø)(As) (= 70.3 kcal mole(-1)). In the calculations, the fully-relativistic small-core effective core potential (ECP10MDF) was used for As. Contributions from outer core correlation of As 3d(10) electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d(10) electrons. Basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were used in RCCSD(T) calculations and computed relative electronic energies were extrapolated to the complete basis set (CBS) limit. For the simplified, explicitly correlated UCCSD(T)-F12x calculations, basis sets of up to quadruple-zeta (QZ) quality were employed. Based on the RCCSD(T)/CBS benchmark values, the reliability of available theoretical and experimental values have been assessed., (This journal is © the Owner Societies 2011)

RCCSD(T) and/or CASSCF/MRCI calculations were carried out on the X(2)B(1) state of AsF(2), the X(1)A(1), ã(3)B(1) and A(1)B(1) states of AsF(2)(+), and the X(1)A(1) state of AsF(2)(-) employing the fully-relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d(10) electrons. In addition, simplified, explicitly correlated RHF/UCCSD(T)-F12x calculations were also performed employing different atomic orbital basis sets, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimates of the adiabatic ionization energies (AIE(0)) of AsF(2)(X(2)B(1)) to the X(1)A(1) and ã(3)B(1) states of AsF(2)(+), including corrections for zero-point vibrational energy (DeltaZPE), are 9.099(8) and 13.290(22) eV respectively. The best estimated electron affinity (EA(0)) of AsF(2) is 1.182(16) eV, also including Delta(ZPE). These are currently the most reliable AIE(0) and EA(0) values for AsF(2). Potential energy functions (PEFs) of the X(2)B(1) state of AsF(2), the X(1)A(1) and ã(3)B(1) states of AsF(2)(+) and X(1)A(1) state of AsF(2)(-) were computed at RCCSD(T)/aug-cc-pV5Z, RCCSD(T)/aug-cc-pCV5Z and RHF/UCCSD(T)-F12a/aug-cc-pCVTZ levels. These PEFs were employed in variational calculations of anharmonic vibrational wavefunctions, which were then utilised to calculate Franck-Condon factors (FCFs), using a method which includes allowance for anharmonicity and Duschinsky rotation. The computed FCFs were used to simulate the first two bands in the photoelectron spectrum of AsF(2) and the first band in the photodetachment spectrum of AsF(2)(-), both yet to be recorded. The simulated spectra obtained using different sets of PEFs were found to be almost identical, suggesting that the simplified explicitly correlated UCCSD(T)-F12x method with a relatively small basis set can be a reliable alternative to the conventional RCCSD(T) correlation methods with a relatively large basis set, but at a significantly lower cost.

Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the X[combining tilde]1A1 state of HfO2 and the X[combining tilde]2A1 state of HfO2- were computed, employing the quasi-relativistic effective core potential, ECP60MWB, and an associated contracted [13s6p6d4f3g2h] basis set designed for Hf, and the augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set for O. Based on the differences between the computed r0 and re geometrical parameters obtained from the PEF, and available experimentally derived r0 geometrical parameters of the X[combining tilde]1A1 state of HfO2, the experimental re geometrical parameters of the X[combining tilde]1A1 state of HfO2 were estimated as:-re(HfO)=1.7751 A and thetae(OHfO)=107.37 degrees. In addition, Franck-Condon factors for the HfO2 (X[combining tilde]1A1)+e<--HfO2- (X[combining tilde]2A1) electron detachment process, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the HfO2 (X[combining tilde]1A1)+e<--HfO2- (X[combining tilde]2A1) photodetachment band of HfO2-. Employing the estimated experimental re geometrical parameters of the X[combining tilde]1A1 state of HfO2 obtained in this work, the iterative Franck-Condon analysis (IFCA) procedure was carried out to optimize the geometrical parameters of the X[combining tilde]2A1 state of HfO2- until the simulated spectrum matched best with the experimental 355 nm photodetachment spectrum of W. Zheng, et. al., J. Phys. Chem. A, 1998, 102, 9129. The equilibrium geometrical parameters of X[combining tilde]2A1 state of HfO2- derived via the IFCA procedure are re(HfO)=1.823 A and thetae(OHfO)=111.5 degrees. Further calculations on low-lying triplet states of HfO2 gave adiabatic electronic energies (Te's) of, and vertical excitation energies (Tvert's) to, the ã 3B2, b[combining tilde]3B1, c[combining tilde]3A1 and d[combining tilde]3A2 states of HfO2 (from the X[combining tilde]1A1 state of HfO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the X[combining tilde]2A1 state of HfO2-.

Geometry optimization and harmonic vibrational frequency calculations have been carried out on low-lying doublet and quartet electronic states of stannous (tin(II)) dichloride anion (SnCl(2)(-)) employing the CASSCF and RCCSD(T) methods. The small-core fully-relativistic effective core potential, ECP28MDF, was used for Sn in these calculations, together with valence basis sets of up to augmented correlation-consistent polarized-valence quintuple-zeta (aug-cc-pV5Z) quality. The ground electronic state of SnCl(2)(-) is determined to be the X(2)B(1) state, with the A(2)B(2) and ã(4)Sigma state, calculated to be ca. 1.50 and 2.72 eV higher in energy respectively. The electron affinities of the X(1)A(1) and ã(3)B(1) states of SnCl(2) have been computed to be 1.568+/-0.007 and 4.458+/-0.002 eV respectively, including contributions of core correlation and extrapolation to the complete basis set limit. The SnCl(2) (X(1)A(1)) + e <-- SnCl(2)(-) (X(2)B(1)) and SnCl(2) (ã(3)B(1)) + e <-- SnCl(2)(-) (X(2)B(1)) photodetachment bands have been simulated with computed Franck-Condon factors, which include an allowance for anharmonicity and Duschinsky rotation.