skip to main content

This content will become publicly available on October 7, 2023

Title: Benchmarking the semi-stochastic CC( P ; Q ) approach for singlet–triplet gaps in biradicals
We recently proposed a semi-stochastic approach to converging high-level coupled-cluster (CC) energetics, such as those obtained in the CC calculations with singles, doubles, and triples (CCSDT), in which the deterministic CC( P; Q) framework is merged with the stochastic configuration interaction Quantum Monte Carlo propagations [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)]. In this work, we investigate the ability of the semi-stochastic CC( P; Q) methodology to recover the CCSDT energies of the lowest singlet and triplet states and the corresponding singlet–triplet gaps of biradical systems using methylene, (HFH) − , cyclobutadiene, cyclopentadienyl cation, and trimethylenemethane as examples.
; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
The Journal of Chemical Physics
Page Range or eLocation-ID:
Sponsoring Org:
National Science Foundation
More Like this
  1. A novel pyranine derivative, Et HPTA-OH, was synthesized via the substitution of the anionic sulfonate groups with neutral diethylsulfonamide groups. The photophysical and photochemical properties of Et HPTA-OH were studied using photoluminescence quenching and transient absorption spectroscopy. The singlet state of Et HPTA-OH was found to be highly photoacidic (p K a * = 8.74 in acetonitrile). A series of aniline and pyridine bases were used to investigate excited-state proton transfer (ESPT) from singlet Et HPTA-OH, and rate constants for singlet quenching via ESPT were determined ( k q = 5.18 × 10 9 to 1.05 × 10 10 M −1 s −1 ). Et HPTA-OH was also found to exhibit a long-lived triplet state which reacts through a triplet–triplet annihilation (TTA) process to reform singlet Et HPTA-OH on timescales of up to 80 μs. Detection of ESPT photoproducts on timescales comparable to that of TTA singlet regeneration provides strong evidence for photoacidic behavior stemming from the regenerated singlet Et HPTA-OH.
  2. Dynamic nuclear polarization (DNP) is widely used to enhance solid state nuclear magnetic resonance (NMR) sensitivity. Its efficiency as a generic signal-enhancing approach for liquid state NMR, however, decays rapidly with magnetic field B 0 , unless mediated by scalar interactions arising only in exceptional cases. This has prevented a more widespread use of DNP in structural and dynamical solution NMR analyses. This study introduces a potential solution to this problem, relying on biradicals with exchange couplings J ex of the order of the electron Larmor frequency ω E . Numerical and analytical calculations show that in such J ex ≈ ± ω E cases a phenomenon akin to that occurring in chemically induced DNP (CIDNP) happens, leading to different relaxation rates for the biradical singlet and triplet states which are hyperfine-coupled to the nuclear α or β states. Microwave irradiation can then generate a transient nuclear polarization build-up with high efficiency, at all magnetic fields that are relevant in contemporary NMR, and for all rotational diffusion correlation times that occur in small- and medium-sized molecules in conventional solvents.
  3. In this work, we investigated bonding features of 15 ruthenium(II) nitrile complexes of the type [Ru(tpy)(L)-(CH 3 CN)] n+ , containing the tridentate tpy ligand (tpy = 2,2′:6′,2″-terpyridine) and various bidentate ancillary ligands L; 12 compounds originally synthesized by Loftus et al. [J. Phys. Chem. C 123, 10291–10299 (2019)] and three new complexes. We utilized local vibrational force constants derived from the local mode theory as a quantitative measure of bond strength complemented with the topological analysis of the electron density and the natural bond orbital analysis. Loftus et al. suggested that nitrile dissociation occurs after light induced singlet–triplet transition of the original complexes and they used as a measure of nitrile release efficiency quantum yields for ligand exchange in water. They observed larger quantum yields for complexes with smaller singlet–triplet energy gaps. The major goal of this work was to assess how the Ru–NC and Ru–L bond strengths in these 15 compounds relate to and explain the experimental data of Loftus et al., particularly focusing on the question whether there is a direct correlation between Ru–NC bond strength and measured quantum yield. Our study provides the interesting result that the compounds with the highest quantum yields also have themore »strongest Ru–NC bonds suggesting that breaking the Ru–NC bond is not the driving force for the delivery process rather than the change of the metal framework as revealed by first results of a unified reaction valley approach investigation of the mechanism. Compounds with the highest quantum yield show larger electronic structure changes upon singlet–triplet excitation, i.e., larger changes in bond strength, covalency, and difference between the singlet and triplet HOMOs, with exception of the compound 12. In summary, this work provides new insights into the interplay of local properties and experimental quantum yields forming in synergy a useful tool for fine tuning of existing and future design of new nitrile releasing ruthenium compounds. We hope that this work will bring theoretical and experimental studies closer together and serves as an incubator for future collaboration between computational chemists and their experimental colleagues.« less
  4. Hypohalous acids (HOX) are a class of molecules that play a key role in the atmospheric seasonal depletion of ozone and have the ability to form both hydrogen and halogen bonds. The interactions between the HOX monomers (X = F, Cl, Br) and water have been studied at the CCSD(T)/aug-cc-pVTZ level of theory with the spin free X2C-1e method to account for scalar relativistic effects. Focal point analysis was used to determine CCSDT(Q)/CBS dissociation energies. The anti hydrogen bonded dimers were found with interaction energies of −5.62 kcal mol −1 , −5.56 kcal mol −1 , and −4.97 kcal mol −1 for X = F, Cl, and Br, respectively. The weaker halogen bonded dimers were found to have interaction energies of −1.71 kcal mol −1 and −3.03 kcal mol −1 for X = Cl and Br, respectively. Natural bond orbital analysis and symmetry adapted perturbation theory were used to discern the nature of the halogen and hydrogen bonds and trends due to halogen substitution. The halogen bonds were determined to be weaker than the analogous hydrogen bonds in all cases but close enough in energy to be relevant, significantly more so with increasing halogen size.
  5. The anionic products following (H + H + ) abstraction from o -, m -, and p -methylphenol (cresol) are investigated using flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometry and anion photoelectron spectroscopy (PES). The PES of the multiple anion isomers formed in this reaction are reported, including those for the most abundant isomers, o -, m - and p -methylenephenoxide distonic radical anions. The electron affinity (EA) of the ground triplet electronic state of neutral m -methylenephenoxyl diradical was measured to be 2.227 ± 0.008 eV. However, the ground singlet electronic states of o - and p -methylenephenoxyl were found to be significantly stabilized by their resonance forms as a substituted cyclohexadienone, resulting in measured EAs of 1.217 ± 0.012 and 1.096 ± 0.007 eV, respectively. Upon electron photodetachment, the resulting neutral molecules were shown to have Franck–Condon active ring distortion vibrational modes with measured frequencies of 570 ± 180 and 450 ± 80 cm −1 for the ortho and para isomers, respectively. Photodetachment to excited electronic states was also investigated for all isomers, where similar vibrational modes were found to be Franck–Condon active, and singlet–triplet splittings are reported. The thermochemistry of these molecules was investigated using FA-SIFTmore »combined with the acid bracketing technique to yield values of 341.4 ± 4.3, 349.1 ± 3.0, and 341.4 ± 4.3 kcal mol −1 for the o -, m -, and p -methylenephenol radicals, respectively. Construction of a thermodynamic cycle allowed for an experimental determination of the bond dissociation energy of the O–H bond of m -methylenephenol radical to be 86 ± 4 kcal mol −1 , while this bond is significantly weaker for the ortho and para isomers at 55 ± 5 and 52 ± 5 kcal mol −1 , respectively. Additional EAs and vibrational frequencies are reported for several methylphenyloxyl diradical isomers, the negative ions of which are also formed by the reaction of cresol with O − .« less