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1.
J Am Chem Soc ; 146(10): 6866-6879, 2024 Mar 13.
Article in English | MEDLINE | ID: mdl-38437011

ABSTRACT

Activity descriptors are a powerful tool for the design of catalysts that can efficiently utilize H2 with minimal energy losses. In this study, we develop the use of hydricity and H- self-exchange rates as thermodynamic and kinetic descriptors for the hydrogenation of ketones by molecular catalysts. Two complexes with known hydricity, HRh(dmpe)2 and HCo(dmpe)2, were investigated for the catalytic hydrogenation of ketones under mild conditions (1.5 atm and 25 °C). The rhodium catalyst proved to be an efficient catalyst for a wide range of ketones, whereas the cobalt catalyst could only hydrogenate electron-deficient ketones. Using a combination of experiment and electronic structure theory, thermodynamic hydricity values were established for 46 alkoxide/ketone pairs in both acetonitrile and tetrahydrofuran solvents. Through comparison of the hydricities of the catalysts and substrates, it was determined that catalysis was observed only for catalyst/ketone pairs with an exergonic H- transfer step. Mechanistic studies revealed that H- transfer was the rate-limiting step for catalysis, allowing for the experimental and computation construction of linear free-energy relationships (LFERs) for H- transfer. Further analysis revealed that the LFERs could be reproduced using Marcus theory, in which the H- self-exchange rates for the HRh/Rh+ and ketone/alkoxide pairs were used to predict the experimentally measured catalytic barriers within 2 kcal mol-1. These studies significantly expand the scope of catalytic reactions that can be analyzed with a thermodynamic hydricity descriptor and firmly establish Marcus theory as a valid approach to develop kinetic descriptors for designing catalysts for H- transfer reactions.

2.
Inorg Chem ; 63(11): 4819-4827, 2024 Mar 18.
Article in English | MEDLINE | ID: mdl-38437739

ABSTRACT

Progress toward the closure of the nuclear fuel cycle can be achieved if satisfactory separation strategies for the chemoselective speciation of the trivalent actinides from the lanthanides are realized in a nonproliferative manner. Since Kolarik's initial report on the utility of bis-1,2,4-triazinyl-2,6-pyridines (BTPs) in 1999, a perfect complexant-based, liquid-liquid separation system has yet to be realized. In this report, a comprehensive performance assessment for the separation of 241Am3+ from 154Eu3+ as a model system for spent nuclear fuel using hydrocarbon-actuated alkoxy-BTP complexants is described. These newly discovered complexants realize gains that contemporary aryl-substituted BTPs have yet to achieve, specifically: long-term stability in highly concentrated nitric acid solutions relevant to the low pH of unprocessed spent nuclear fuel, high DAm over DEu in the economical, nonpolar diluent Exxal-8, and the demonstrated capacity to complete the separation cycle with high efficiency by depositing the chelated An3+ to the aqueous layer via decomplexation of the metal-ligand complex. These soft-N-donor BTPs are hypothesized to function as bipolar complexants, effectively traversing the organic/aqueous interface for effective chelation and bound metal/ligand complex solubility. Complexant design, separation assays, spectroscopic analysis, single-crystal X-ray crystallographic data, and DFT calculations are reported.

3.
J Am Chem Soc ; 146(6): 3773-3784, 2024 Feb 14.
Article in English | MEDLINE | ID: mdl-38301281

ABSTRACT

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from the bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H2 followed by O2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate-determining. Electronic-structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from one involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H2 and, alternatively, with D2 on the cluster incorporating the dioxygen ligands and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H2 with D2 to give HD. We posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

4.
J Phys Chem A ; 127(50): 10600-10612, 2023 Dec 21.
Article in English | MEDLINE | ID: mdl-38085654

ABSTRACT

The aqueous electron affinity and aqueous reduction potentials for F•, Cl•, Br•, I•, OH•, SH•, SeH•, TeH•, ClO•, BrO•, and IO• were calculated using electronic structure methods for explicit cluster models coupled with a self-consistent reaction field (SMD) to treat the aqueous solvent. Calculations were conducted using MP2 and correlated molecular orbital theory up to the CCSD(T)-F12b level for water tetramer clusters and MP2 for octamer cluster. Inclusion of explicit waters was found to be important for accurately predicting the redox potentials in a number of cases. The calculated reduction potentials for X• and ChH• were predicted to within ∼0.1 V of the reported literature values. Fluorine is anomalous due to abstraction of a hydrogen from one of the surrounding water molecules to form a hydroxyl radical and hydrogen fluoride, so its redox potential was calculated using only an implicit model. Larger deviations from experiment were predicted for ClO• and BrO•. These deviations are due to the free energy of solvation of the anion being too negative, as found in the pKa calculations, and that for the neutral being too positive with the current approach.

5.
J Phys Chem A ; 127(51): 10838-10850, 2023 Dec 28.
Article in English | MEDLINE | ID: mdl-38109706

ABSTRACT

The ligand binding energies (LBEs) of N-heterocyclic carbenes (NHCs) and CH2 and CF2 adducts with group 1, 2, 10, and 11 metals and complexes with metals from these groups are predicted at the coupled cluster CCSD(T) level of theory by using density functional theory optimized geometries. The differences in LBEs as a function of the metal and the types of bonding interactions as well as the type of carbene are described. The bonding between the alkali cations and alkaline earth dications is predominantly ionic with a linear correlation between the LBEs and the cation hardness. In contrast, the bonding behaviors of the group 10 and 11 metals and metal complexes have only a weak, indirect correlation between the LBEs and the metal hardness. The difference in bonding behavior between the groups of metals arises due to the accessibility of electron donation between the ligand and the metal in the transition metal complexes, which results in more covalent-like bonding behavior. The presence of the methyl groups on the NHC nitrogen results in only slightly more delocalized charge from the metal onto the ring, but there is significant redistribution of the charge on the ring. Saturation of the NHC ring had a much smaller effect on how the charge was distributed on the ring. The analysis of the bonding behavior of NHCs with various metal groups enables improved understanding of carbene-metal interactions to inform rational design of NHC-based systems.

6.
J Chem Phys ; 159(24)2023 Dec 28.
Article in English | MEDLINE | ID: mdl-38131483

ABSTRACT

The reactions of Cl, Br, and I with Nan=2,3 produced in a supersonic expansion form Na2* and Na* excited states extending across the visible and ultraviolet regions. Emission in the region extending from 410 to 600 nm indicates selectively formed excited state Na2 emission features. Experimental evidence suggests that this emission is associated with Na3 + X reactions. Broadband (0.5 cm-1) laser measurements demonstrate gain (population inversion) for select features at∼524-528(1%), ∼492(0.3%), and ∼458.7-461(0.8%) nm. Single mode (0.007 cm-1) measurements extending from 528.03 to 527.63 nm demonstrate amplification involving five to six individual rovibronic levels with a maximum gain close to 3% recorded at 527.9 nm. The observed gain is associated with select transitions from levels of the Na2 11Πu state populated, via identified curve crossings, through collision induced transfer from long-lived Na2 21Σg+ and 11Πg reservoir states. Collision induced population buildup in the lowest vibrational levels of these reservoir states and collision induced transfer to the Na2 11Πu state create a population inversion in transitions to the X 1Σg+ state of Na2. The observed amplification is aided by rapid vibrational and rotational relaxation in both the Na2 ground and excited reservoir states producing amplifiers in the visible region like the HF amplifier in the infrared. This study suggests the importance of reaction populated and energy storing long-lived reservoir states in small sodium molecule combustion processes and indicates the potential for providing new short wavelength visible and ultraviolet amplifiers for future laser-based chemical propulsion concepts.

7.
J Phys Chem A ; 127(47): 9985-9994, 2023 Nov 30.
Article in English | MEDLINE | ID: mdl-37967283

ABSTRACT

The interactions between group 1 and 11 monocations and group 2 dications with triphenylphosphine were studied by using a combination of correlated molecular orbital theory and density functional theory. Two binding modes were found: the front side (phosphorus lone pair) and back side (phenyl rings). Group 1 and 2 cations prefer binding to the π system rather than to the lone pair of the phosphorus atom, and their ligand binding energies (LBEs) correlate with the atomic ionic radii as well as the hardness of the atomic ion. Group 11 monocations prefer binding to the lone pair of the phosphorus atom, and their LBEs are correlated with the hardness of the cation but exhibit a different trend than for the groups 1 and 2 cations. The LBEs of the cations with C2H4, C6H6, and C6H5PH2 are also reported to aid in the analysis of the cation-π interactions and the influence of the PH2 substituent on the energy of this interaction. The LBEs for binding to C2H4 and C6H6 are the most complete and reliable set of values for these species.

8.
J Phys Chem A ; 127(45): 9541-9549, 2023 Nov 16.
Article in English | MEDLINE | ID: mdl-37934079

ABSTRACT

Transition metal oxide (TMO) clusters are being studied for their ability to absorb acid gases generated by energy production processes. The interaction of SO3, a byproduct of common industrial processes, with group 4 metal (Ti, Zr, and Hf) oxide nanoclusters, has been predicted using electronic structure methods. The calculations were done at the density functional theory (DFT) and correlated molecular orbital coupled cluster singles and doubles CCSD(T) theory levels. There is a reasonable agreement between the DFT/ωB97x-D energies with the CCSD(T) results. SO3 is predicted to strongly chemisorb to these clusters, as do NO2 and CO2. For SO3, these chemisorption processes favor binding to TMO clusters as SO42- sulfate in both the terminal and bridging configurations. It is predicted that SO3 fully extracts the bridging oxygen from the TMO lattice to form bridging SO42-. This is favorable because of the lower S-O bond dissociation energy of SO3, whereas other acid gases add across the bridging oxygen because of their higher A-O bond dissociation energy. SO3 is capable of physisorption as long as an exposed metal center is present in the lattice. If a metal center has a terminal oxo-group, then SO3 will prefer the SO42- configuration. An approximately linear relationship exists between the physisorption energy and proton affinity for rows 2 and 3 elements.

9.
J Phys Chem A ; 127(48): 10171-10183, 2023 Dec 07.
Article in English | MEDLINE | ID: mdl-37991507

ABSTRACT

Acid gases including CO2, OCS, CS2, and SO2 are emitted by industrial processes such as natural gas production or power plants, leading to the formation of acid rain and contributing to global warming as greenhouse gases. An important technological challenge is to capture acid gases and transform them into useful products. The capture of CO2, CS2, SO2, and OCS by ring expansion of saturated and unsaturated substituted nitrogen-strained ring heterocycles was computationally investigated at the G3(MP2) level. The effects of fluorine, methyl, and phenyl substituents on N and/or C were explored. The reactions for the capture CO2, CS2, SO2, and OCS by 3- and 4-membered N-heterocycles are exothermic, whereas ring expansion reactions with 5-membered rings are thermodynamically unfavorable. Incorporation of an OCS into the ring leads to the amide product being thermodynamically favored over the thioamide. CS2 and OCS capture reactions are more exothermic and exergonic than the corresponding CO2 and SO2 capture reactions due to bond dissociation enthalpy differences. Selected reaction energy barriers were calculated and correlated with the reaction thermodynamics for a given acid gas. The barriers are highest for CO2 and OCS and lowest for CS2 and SO2. The ability of a ring to participate in acid gas capture via ring expansion is correlated to ring strain energy but is not wholly dependent upon it. The expanded N-heterocycles produced by acid gas capture should be polymerizable, allowing for upcycling of these materials.

10.
Antiviral Res ; 219: 105733, 2023 11.
Article in English | MEDLINE | ID: mdl-37858763

ABSTRACT

Herpes is a contagious life-long infection with persistently high incidence and prevalence, causing significant disease worldwide. Current therapies have efficacy against active HSV infections but no impact on the latent viral reservoir in neurons. Thus, despite treatment, disease recurs from latency and the infectious potential remains unaffected within patients. Here, efficacy of the helicase-primase inhibitor (HPI) IM-250 against chronic neuronal HSV infections utilizing two classic herpes in vivo latency/reactivation animal models (intravaginal guinea pig HSV-2 infection model and ocular mouse HSV-1 infection model) is presented. Intermittent therapy of infected animals with 4-7 cycles of IM-250 during latency silences subsequent recurrences analyzed up to 6 months. In contrast to common experience, our studies show that the latent reservoir is indeed accessible to antiviral therapy altering the latent viral reservoir such that reactivation frequency can be reduced significantly by prior IM-250 treatment. We provide evidence that antiviral treatment during HSV latency can reduce future reactivation from the latent reservoir, supporting a conceptual shift in the antiviral field, and reframing what is achievable with respect to therapy of latent neuronal HSV infections.


Subject(s)
Herpes Simplex , Herpesvirus 1, Human , Humans , Animals , Mice , Guinea Pigs , DNA Primase , Virus Latency/physiology , Herpes Simplex/drug therapy , Herpesvirus 1, Human/physiology , Disease Models, Animal , Antiviral Agents/pharmacology , Antiviral Agents/therapeutic use
11.
J Phys Chem A ; 127(32): 6732-6748, 2023 Aug 17.
Article in English | MEDLINE | ID: mdl-37549315

ABSTRACT

The energetics of the hydrolysis reactions for high oxidation states of the dimeric actinide species Th2IVO4, Pa2VO5, and U2VIO6 were calculated at the CCSD(T) level and those for triplet Np2VIO6 at the B3LYP level. Hydrolysis is initiated by the formation of a Lewis acid/base adduct with H2O (physisorbed product), followed by a proton transfer to form a dihydroxide molecule (chemisorbed product); this process was repeated until the initial actinide oxide is fully hydrolyzed. For Th2O4, hydrolysis (chemisorption) by the initial and subsequent H2O molecules prefers proton transfer to terminal oxo groups before the bridge oxo groups. The overall Th2O4 hydration pathway is exothermic with chemisorbed products preferred over the physisorption products, and the fully hydrolyzed Th2(OH)8 can form exothermically. Hydrolysis of Pa2O5 forms isomers of similar energies with no initial preference for bridge or terminal hydroxy groups. The most exothermic hydrolysis product for Pa is Pa2O(OH)8 and the most stable species is Pa2O(OH)8(H2O). Hydrolysis of U2O6 and Np2O6 with strong [O═An═O]2+ actinyl groups occurs first at the bridging oxygens rather than at the terminal oxo groups. The U2O6 and Np2O6 pathways predict hydrated products to be more favored than hydrolyzed products, as more H2O molecules are added. The stability of the U and Np clusters is predicted to decrease with increasing number of hydroxyl groups. The most stable species on the hydration reaction coordinate for U and Np is An2O3(OH)6(H2O).

12.
Angew Chem Int Ed Engl ; 62(39): e202307218, 2023 Sep 25.
Article in English | MEDLINE | ID: mdl-37438320

ABSTRACT

The purely chemical synthesis of fluorine is a spectacular reaction which for more than a century had been believed to be impossible. In 1986, it was finally experimentally achieved, but since then this important reaction has not been further studied and its detailed mechanism had been a mystery. The known thermal stability of MnF4 casts serious doubts on the originally proposed hypothesis that MnF4 is thermodynamically unstable and decomposes spontaneously to a lower manganese fluoride and F2 . This apparent discrepancy has now been resolved experimentally and by electronic structure calculations. It is shown that the reductive elimination of F2 requires a large excess of SbF5 and occurs in the last reaction step when in the intermediate [SbF6 ][MnF2 ][Sb2 F11 ] the addition of one more SbF5 molecule to the [SbF6 ]- anion generates a second tridentate [Sb2 F11 ]- anion. The two tridentate [Sb2 F11 ]- anions then provide six fluorine bridges to the Mn atom thereby facilitating the reductive elimination of the two fluorine ligands as F2 .

13.
J Phys Chem A ; 127(16): 3614-3624, 2023 Apr 27.
Article in English | MEDLINE | ID: mdl-37043178

ABSTRACT

Dehydration and dehydrogenation of an ethanol molecule on (TiO2)n, n = 2-4, nanoclusters were studied at the correlated molecular orbital theory CCSD(T)/aug-cc-pVDZ(-PP(Ti)) level using density functional theory B3LYP/DZVP2-optimized geometries. Physisorption and chemisorption of ethanol at the bridge Ti site on the trimer and tetramer are thermodynamically preferred over these reactions at the Ti site with a terminal Ti═O. Two possible lowest energy reaction coordinates of dehydration were predicted for the dimer and trimer where the ß hydrogen on ethanol transfers to the adjacent terminal oxygen, or to the adjacent bidentate oxygen. Only the latter reaction coordinate was predicted to be the lowest energy one for the tetramer. Removal of ethylene from the (TiO2)nOH2-C2H4 complex for n = 2-4 at 0 K requires 2-7 kcal/mol. For dehydrogenation, transfer of the α hydrogen to the adjacent Ti atom results in the lowest energy reaction coordinate following a proton-coupled electron-transfer (PCET) process. Removal of the acetaldehyde molecule requires 14-26 kcal/mol from the (TiO2)nH2-C2H4O complex. Loss of H2 from the (TiO2)nH2 complex requires 5-8 kcal/mol. Dehydration and dehydrogenation of one ethanol molecule occur below the reactant asymptote for (TiO2)n, n = 2-4, whereas for (WO3)3 and (MoO3)3, two ethanol molecules are required for this process to be below the reactant asymptote. Dehydration of ethanol is thermodynamically preferred over dehydrogenation on (TiO2)n, n = 2-4. There is an approximate linear correlation of metal Lewis acidity with physisorption of ethanol. A quadratic correlation is predicted between the chemisorption barrier of ethanol and the corresponding proton affinity of oxygen to which the proton is being transferred. There are linear correlations between the basicity of the oxygen site and the acidity of the OH group versus the energy to remove C2H4 from that site. The results for the nanoclusters for n = 3 and 4 are consistent with the experimental results for the reactivity of ethanol on Ti5c4+ rutile TiO2 (110) surface sites.

14.
Phys Chem Chem Phys ; 25(12): 8355-8368, 2023 Mar 22.
Article in English | MEDLINE | ID: mdl-36912479

ABSTRACT

Structures for the mono-, di-, and tri-bridge isomers of M2O5 as well as those for the MO2 and MO3 fragments for M = V, Nb, Ta, and Pa were optimized at the density functional theory (DFT) level. Single point CCSD(T) calculations extrapolated to the complete basis set (CBS) limit at the DFT geometries were used to predict the energetics. The lowest energy dimer isomer was the di-bridge for M = V and Nb and the tri-bridge for M = Ta and Pa. The di-bridge isomers were predicted to be composed of MO2+ and MO3- fragments, whereas the mono- and tri-bridge are two MO2+ fragments linked by an O2-. The heats of formation of M2O5 dimers, as well as MO2 and MO3 neutral and ionic species were predicted using the Feller-Peterson-Dixon (FPD) approach. The heats of formation of the MF5 species were calculated to provide additional benchmarks. Dimerization energies to form the M2O5 dimers are predicted to become more negative going down group 5 and range from -29 to -45 kcal mol-1. The ionization energies (IEs) for VO2 and TaO2 are essentially the same at 8.75 eV whereas the IEs for NbO2 and PaO2 are 8.10 and 6.25 eV, respectively. The predicted adiabatic electron affinities (AEAs) range from 3.75 eV to 4.45 eV for the MO3 species and vertical detachment energies from 4.21 to 4.59 eV for MO3-. The calculated MO bond dissociation energies increase from 143 kcal mol-1 for M = V to ∼170 kcal mol-1 for M = Nb and Ta to ∼200 kcal mol-1 for M = Pa. The M-O bond dissociation energies are all similar ranging from 97 to 107 kcal mol-1. Natural bond analysis provided insights into the types of chemical bonds in terms of their ionic character. Pa2O5 is predicted to behave like an actinyl species dominated by the interactions of approximately linear PaO2+ groups.

15.
J Phys Chem A ; 127(14): 3179-3189, 2023 Apr 13.
Article in English | MEDLINE | ID: mdl-36988907

ABSTRACT

High-level correlated molecular orbital theory calculations have been performed to predict the thermodynamic and electronic properties of diatomic NpH0/+/- and PuH0/+/-. The excited states up to ∼10,000 cm-1 were predicted for these molecules at the multireference SO-CASPT2 level. The inclusion of spin-orbit effects is fundamental to predict the low-lying state ordering. NpH is predicted to have a 5Π0 ground state, and PuH has a 6Π1/2 ground state at the SO-CASPT2 level. The adiabatic electron affinities (AEAs) and ionization energies (IEs) of NpH and PuH were calculated to be 0.389 and 6.156 and 0.396 and 6.296 eV, respectively, using the Feller-Peterson-Dixon approach. The AEA increases going from AcH (0.425 eV) to ThH (0.820 eV) and decreases from ThH to PuH. The IEs of Pa-Np hydrides are close to ∼6.2 eV followed by an increase of 0.14 eV to PuH (6.296 eV). The An-H bond dissociation energy (BDE) decreases from 276.4 (AcH) to 107.1 (PuH) kJ/mol; the BDE(NpH) is ∼80 kJ/mol higher than that of PuH. Natural bond orbital calculations show that the bond character for these molecules is mainly ionic, An+H-. The additional electron in NpH- and PuH- populates the 6d orbital, and NpH+ and PuH+ are formed by the removal of a 7s electron. The current work in conjunction with prior work on the AcH to UH in different charge states provides insights into how these properties change across the actinide series.

16.
J Phys Chem A ; 127(7): 1588-1597, 2023 Feb 23.
Article in English | MEDLINE | ID: mdl-36753327

ABSTRACT

The bonding and spectroscopy of the UB0/+/- and WB0/+/- molecules were examined by performing high-level electronic structure calculation on their low-lying electronic states. The calculations were performed at the SO-CASPT2 level to obtain the low-lying excited states and at the FPD level to calculate the adiabatic electronic affinities (AEA), ionization energies (IE), and bond dissociation energies (BDE). Compared to UC and UN, UB has a much denser manifold of states below 1.7 eV. The ground state of UB is predicted to be 8I5/2, and that of WB is 6Π7/2. The calculated IEs of UB and WB are 6.241 and 7.314 eV, respectively, and the corresponding AEAs are 1.160 and 1.422 eV. The BDE of UB is predicted to be 223.1 kJ/mol, which is considerably lower than those predicted for UC and UN and ∼35 kJ/mol lower than the BDE of WB. NBO calculations show that the U and B are connected by two 1-electron π bonds and one 1-electron σ bond with substantial ionic character and a bond order of 1.5. There are three unpaired electrons in the 5f on U. WB has less ionic character than UB with a doubly occupied π bond and a singly occupied σ bond for a bond order of ∼1.5. The results show that the U in UB behaves more like an actinide and the W in WB more like a transition metal.

17.
J Phys Chem A ; 127(1): 240-249, 2023 Jan 12.
Article in English | MEDLINE | ID: mdl-36563176

ABSTRACT

The selective catalytic reduction (SCR) of NO by NH3 on metal oxides plays a key role in minimizing NOx emissions. Electronic structure calculations at the density functional theory level have been performed to predict the vibrational modes of NH3/NH4+ bound to validated cluster models of vanadium oxide bound to a TiO2 surface. Excellent agreement of the scaled calculated values with the observed bands attributed to surface-bound species is found. The presence of NH3 bound to Lewis acid sites and NH4+ bound to Brønsted acid sites when VOH groups are present is supported by our predictions. NH4+ is expected to dominate the spectra even at low concentrations, with predicted intensities 5 to 30 times greater than those predicted for surface-bound NH3. This is particularly evident in the lowest-energy N-H stretches of surface NH4+ due to partial proton transfer interactions with the vanadium oxide surface model. The current work is consistent with experimental vibrational spectroscopy results and does not support the presence of a significant amount of NH2 on the catalyst surface for the SCR reaction on VOx/TiO2. The combined experimental and computational results support the presence of both NH3- and NH4+-type species bound to the surface.

18.
J Phys Chem A ; 126(50): 9392-9407, 2022 Dec 22.
Article in English | MEDLINE | ID: mdl-36508745

ABSTRACT

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC-, and UC+ molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller-Peterson-Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC- and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN+, the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC0/+/- molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f27s1), UC- (5f27s2), and UC+ (5f27s0). The behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.

19.
J Phys Chem A ; 126(49): 9190-9206, 2022 Dec 15.
Article in English | MEDLINE | ID: mdl-36469972

ABSTRACT

Heats of formation and gas phase acidities for the simple acids and their deprotonated anions (A- = F-, Cl-, Br-, I-, OH-, SH-, SeH-, TeH-, OCl-, OBr-, and OI-) were calculated using the Feller-Peterson-Dixon (FPD) method with large basis sets including Douglass-Kroll scalar relativistic corrections. Hydration of the neutral and anionic species was predicted using the supermolecule-continuum approach, resulting in absolute hydration free energies that, when combined with calculated gas phase acidities, produce aqueous acidities and pKa values for these simple acids that are, in general, in excellent agreement with experimental literature values. Absolute hydration free energy values converged quickly in terms of the experimental values for neutral species, requiring only four explicit H2O molecules. HI is anomalous in that it fully dissociates ionically in a water tetramer and was treated without explicit water molecules. The hydration energies of anionic species converged more slowly and were modeled with up to 16 explicit H2O molecules. Calculated values for ΔHf and ΔGgas agree with experimental values within ca. 1.2 kcal/mol, and ΔGaq and ΔΔGhyd agree with experimental values within ca. 2 kcal/mol in most cases.


Subject(s)
Water , Thermodynamics , Anions
20.
J Phys Chem A ; 126(46): 8618-8632, 2022 Nov 24.
Article in English | MEDLINE | ID: mdl-36350720

ABSTRACT

NO2 and NO, which are generated in combustion processes, binding to vanadium oxide clusters including TiO2-supported catalyst models in the selective catalytic reduction (SCR) of NO has been studied by density functional theory and coupled cluster methods. NOx binding on vanadium oxides is predicted to depend on several factors, including the excitation energy of the oxide, ionization energies of both the unbound oxide and the deoxygenated reduced oxide, and the strength of the molecular V-O bonds. NO2 chemisorption occurs either through covalent bond formation in a HONO-like pattern or through abstraction of a metal oxide oxygen leading to the formation of NO3-. Nitrate formation is more favorable than what was predicted for group IVB or group VIB oxides [except (CrO3)n] and is either the lowest energy binding mode or within a few kcal/mol of the lowest mode in all clusters, likely due to the stability of V in the +4 oxidation state. Physisorption on V oxides is very weak. V with 2 oxo groups have a lower excitation energy and a more sterically open geometry which results in strong chemisorption as predicted for group IVB oxides. Tetrahedrally coordinated vanadia with a single oxo group and 3 V-O single bonds are predicted to have significantly higher excitation energies and behave like group VIB oxides such that chemisorption is unlikely and weak physisorption dominates the interaction. In larger clusters, including SCR catalyst models, only tetrahedrally coordinated vanadia are present and NO2 binding is not expected to occur. NO adsorption is weaker overall than NO2 binding and occurs either as physisorption or as chemisorption through the formation of NO2- analogous to nitrate formation in NO2 binding. The ability of NO to bind reflects the patterns predicted for NO2, such that NO is strongly bound vanadia with two V═O groups and only weakly physisorbed when there is a single V═O or none at all.

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