Excited State Hydrogen Transfer Research Articles

Competing Excited-State Hydrogen and Proton-Transfer Processes in 6-Azaindole-S3,4 and 2,6-Diazaindole-S3,4 Clusters (S=H2 O, NH3 ).

Excited state hydrogen (ESHT) and proton (ESPT) transfer reaction pathways in the three and four solvent clusters of 6-azaindole (6AI-S3,4 ) and 2,6-diazaindole (26DAI-S3,4 )(S=H2 O, NH3 ) were computationally investigated to understand the fate of photo-excited biomolecules. The ESHT energy barriers in (H2 O)3 complexes (39.6-41.3 kJmol-1 ) were decreased in (H2 O)4 complexes (23.1-20.2 kJmol-1 ). Lengthening the solvent chain lowered the barrier because of the relaxed transition states geometries with reduced angular strains. Replacing the water molecule with ammonia drastically decreased the energy barriers to 21.4-21.3 kJmol-1 in (NH3 )3 complexes and 8.1-9.5 kJ mol-1 in (NH3 )4 complexes. The transition states were identified as Ha atom attached to the first solvent molecule. The formation of stronger hydrogen bonds in (NH3 )3,4 complexes resulted in facile ESHT reaction than that in the (H2 O)3,4 complexes. The ESPT energy barriers in 6AI-S3,4 and 26DAI-S3,4 were found to range between 40-73 kJmol-1 . The above values were significantly higher than that of the ESHT processes and hence are considered as a minor channel in the process. The effect of N(2) insertion was explored for the very first time in the isolated solvent clusters using local vibrational mode analysis. In DAI-S4 , the higher Ka (Ha ⋯Sa ) values depicted the increased photoacidity of the N(1)-Ha group which may facilitate the hydrogen transfer reaction. However, the increased N(6)⋯Hb bond length elevated the reaction barriers. Therefore, in the ESHT reaction channel, the co-existence of two competing factors led to a marginal/no change in the overall energy barriers due to the N(2) insertion. In the ESPT reaction pathway, the energy barriers showed notable increase upon N(2) insertion because of the increased N(6)⋯Hb bond length.

Excited-state dynamics of deuterated indigo

Indigo, a rich blue dye, is an incredibly photostable molecule that has survived in ancient art for centuries. It is also unique in that it can undergo both an excited-state hydrogen and proton transfer on the picosecond timescale followed by a ground-state back transfer. Previously, we performed gas phase excited-state lifetime studies on indigo to study these processes in a solvent-free environment, combined with excited-state calculations. We found two decay pathways, a fast sub-nanosecond decay and a slow decay on the order of 10 ns. Calculations of the excited-state potential energy surface found that both hydrogen and proton transfer are nearly isoenergetic separated by a 0.1 eV barrier. To further elucidate these dynamics, we now report a study with deuterated indigo, using resonance-enhanced multi-photon ionization and pump-probe spectroscopy with mass spectrometric isotopomer selection. From new calculations of the excited-state potential energy surface, we find sequential double-proton or hydrogen transfer, whereby the trajectory to the second transfer passes a second barrier and then encounters a conical intersection that leads back to the ground state. We find that deuteration only increases the excited-state lifetimes of the fast decay channel, suggesting tunneling through the first barrier, while the slower channel is not affected and may involve a different intermediate state.Graphical abstract

The symmetric quasi-classical model using on-the-fly time-dependent density functional theory within the Tamm–Dancoff approximation

The primary computational challenge when simulating nonadiabatic ab initio molecular dynamics is the unfavourable compute costs of electronic structure calculations with molecular size. Simple electronic structure theories, like time-dependent density functional theory within the Tamm–Dancoff approximation (TDDFT/TDA), alleviate this cost for moderately sized molecular systems simulated on realistic time scales. Although TDDFT/TDA does have some limitations in accuracy, an appealing feature is that, in addition to including electron correlation through the use of a density functional, the cost of calculating analytic nuclear gradients and nonadiabatic coupling vectors is often computationally feasible even for moderately sized basis sets. In this work, some of the benefits and limitations of TDDFT/TDA are discussed and analysed with regard to its applicability as a ‘back-end’ electronic structure method for the symmetric quasi-classical Meyer–Miller model (SQC/MM). In order to investigate the benefits and limitations of TDDFT/TDA, SQC/MM is employed to predict and analyse a prototypical example of excited-state hydrogen transfer in gas-phase malonaldehyde. Then, the ring-opening dynamics of selenophene are simulated, which highlight some of the deficiencies of TDDFT/TDA. Additionally, some new algorithms are proposed that speed up the calculation of analytic nuclear gradients and nonadiabatic coupling vectors for a set of excited electronic states.

Influence of the Solvent Environment on the Ultrafast Relaxation Pathways of a Sunscreen Molecule Diethylamino Hydroxybenzoyl Hexyl Benzoate.

The excited-state dynamics of photoexcited diethylamino hydroxybenzoyl hexyl benzoate (DHHB), a UVA absorber widely used in sunscreen formulations, are studied with transient electronic and vibrational absorption spectroscopy methods in four different solvents. In the polar solvents methanol, dimethyl sulfoxide (DMSO), and acetonitrile, strong stimulated emission (SE) is observed at early time delays after photoexcitation at a near-UV wavelength of λex = 360 nm, and decays with time constants of 420 fs in methanol and 770 fs in DMSO. The majority (∼95%) of photoexcited DHHB returns to the ground state with time constants of 15 ps in methanol and 25 ps in DMSO. In the nonpolar solvent cyclohexane, ∼ 98% of DHHB photoexcited at λex = 345 nm relaxes to the ground state with a ∼ 10 ps time constant, and the SE is weak. DHHB preferentially adopts an enol form in its ground S0 state, but excited state absorption (ESA) bands seen in TEAS are assigned to both the S1-keto and S1-enol forms, indicating a role for ultrafast intramolecular excited state hydrogen transfer (ESHT). This ESHT is inhibited by polar solvents. The two S1 tautomers decay with similar time scales to the observed recovery of ground state population. For molecules that avoid ESHT, torsion around a central C-C bond minimizes the S1-enol energy, quenches the SE, and is proposed to lead to a conical intersection with the S0 state that mediates the ground state recovery. A competing trans-enol isomeric photoproduct is observed as a minor competitor to parent recovery in polar solvents. Evidence is presented for triplet (T1) enol production in polar solvents, and for T1 quenching by octocrylene, a common UVB absorber sunscreen additive. The T1 keto form is observed in cyclohexane solution.

Revealing the role of excited state proton transfer (ESPT) in excited state hydrogen transfer (ESHT): systematic study in phenol-(NH3) n clusters.

Excited State Hydrogen Transfer (ESHT), proposed at the end of the 20th century by the corresponding authors, has been observed in many neutral or protonated molecules and become a new paradigm to understand excited state dynamics/photochemistry of aromatic molecules. For example, a significant number of photoinduced proton-transfer reactions from X–H bonds have been re-defined as ESHT, including those of phenol, indole, tryptophan, aromatic amino acid cations and so on. Photo-protection mechanisms of biomolecules, such as isolated nucleic acids of DNA, are also discussed in terms of ESHT. Therefore, a systematic and up-to-date description of ESHT mechanism is important for researchers in chemistry, biology and related fields. In this review, we will present a general model of ESHT which unifies the excited state proton transfer (ESPT) and the ESHT mechanisms and reveals the hidden role of ESPT in controlling the reaction rate of ESHT. For this purpose, we give an overview of experimental and theoretical work on the excited state dynamics of phenol–(NH3)n clusters and related molecular systems. The dynamics has a significant dependence on the number of solvent molecules in the molecular cluster. Three-color picosecond time-resolved IR/near IR spectroscopy has revealed that ESHT becomes an electron transfer followed by a proton transfer in highly solvated clusters. The systematic change from ESHT to decoupled electron/proton transfer according to the number of solvent molecules is rationalized by a general model of ESHT including the role of ESPT.

Photoisomerization-mechanism-associated excited-state hydrogen transfer in 2'-hydroxychalcone revealed by on-the-fly trajectory surface-hopping molecular dynamics simulation.

By performing global-switching on-the-fly trajectory surface-hopping molecular dynamics simulation at the OM2/MRCI (14,15) quantum level, we probed the S3(ππ*) photoisomerization mechanisms associated with excited-state intramolecular hydrogen transfer for 2'-hydroxychalcone (2HC) within the interwoven conical intersection networks from four singlet electronic states (S3, S2, S1, and S0). The simulated quantum yields of 0.03 for cis-to-trans and zero for trans-to-cis photoisomerization were due to almost all the conical intersections being localized either in the cis-2HC or in trans-2HC region, and there was little chance for sampling trajectories to reach the rotation conical intersection (S1/S0) in between cis-2HC and trans-2HC that is key for reactive isomerization. The potential energy well on the S1 state in the trans-2HC region prevents trajectories from trans-to-cis photoisomerization, while the fact there is no well on S1 state in cis-2HC region opens a few chances for trajectories to reach the rotation conical intersections. The present simulation found that excited-state intramolecular hydrogen transfers in 2HC have a negative impact for reactive isomerization, and that hydrogen transfers take place on the S1 state, while back-transfer on the S0 state prevents sampling trajectories reaching rotational conical intersections. It was realized that it could be possible to enhance the quantum yield of 2HC photoisomerization by suppressing the hydrogen transfer (such as by changing an electron-donating substitution or adjusting the substitution position to decrease the acidity of the phenol group). From a perspective view of the potential energy surfaces, the theoretical design of such 2HC derivatives could enhance (control) the quantum yield by shifting the conical intersections away from the cis- and trans-region.

Excited state hydrogen transfer dynamics in phenol-(NH3)2 studied by picosecond UV-near IR-UV time-resolved spectroscopy.

Time-evolutions of excited state hydrogen transfer (ESHT) in phenol (PhOH)-(NH3)2 clusters have been measured by three-color picosecond (ps) ultraviolet (UV)-near infrared (NIR)-UV pump-probe ion dip spectroscopy. The formation of a reaction product, ˙NH4NH3, is detected by its NIR absorption due to a 3p-3s Rydberg transition. The ESHT reactions from all of the vibronic levels show biexponential time-evolutions, even from the S1 origin. Based on the biexponential time-evolution, it is suggested that there is a second reaction path via the triplet πσ* state, which gives the slow component. The fast time-evolution of the ESHT reaction from the S1 origin is measured to be 268 ps, which is 10-times slower than that in PhOH-(NH3)3, and a higher barrier between the ππ* and reactive πσ* states is suggested. The size dependence of the ESHT reaction rates is discussed based on a potential distortion due to the proton transferred state in the ππ* potential surface.

Electron-proton transfer mechanism of excited-state hydrogen transfer in phenol−(NH3)n (n = 5) studied by delayed ionization detected femtosecond time-resolved NIR spectroscopy

The reaction mechanism of a hydrogen transfer reaction has a fundamental importance in wide ranges of chemistry, such as redox reactions and enzymatic reactions. The excited-state hydrogen transfer (ESHT) of phenol–(NH3)n clusters is a benchmark system to study solvation effects on the ESHT reaction mechanism. Recently, we reported that the mechanism of the ESHT reaction changes to electron–proton decoupled transfer for phenol–(NH3)5, from a concerted hydrogen atom transfer for clusters with n < 5, based on observations of picosecond time-resolved NIR/IR spectroscopy (Miyazaki et al., 2018). However, the dynamics of the initial electron-transfer process has not been addressed because the rate is faster than the time-resolution of the picosecond time-resolved measurement. In this study, femtosecond time-resolved NIR spectroscopy was applied to the phenol–(NH3)5 to elucidate the initial electron-transfer process. Time evolutions probed in the range of 6000–9000 cm−1 detected two rise components that can be ascribed to electronic absorptions of the Franck-Condon region of the excitation and the transient charge-transfer complex, respectively. A kinetic analysis determined the time-scale of the initial charge-transfer process to be τCT = 370 ± 55 fs. The fast reaction time supports (almost) a barrier-less charge transfer process predicted by a theoretical calculation that shows solvation-induced strong mixing of ππ*-πσ* states.

The π-conjugation length determines the fluorescence quenching mechanism of aromatic aldehydes in water

Water-soluble distyrylbenzene-based aldehydes are excellent fluorescence turn-on indicators for amine detection, since they are themselves non-fluorescent in water. Here, the fluorescence quenching mechanisms of aldehydes with systematically increasing π-systems are investigated in an aqueous environment using quantum chemical methods. Although the aldehydes are structurally related, with each extension of the π-system the fluorescence quenching mechanism changes from excited-state hydrogen transfer to trans→cis isomerization and nπ∗ state-mediated intersystem crossing, until the aldehydes become fluorescent in water. For distyrylbenzene aldehyde, nπ∗ mediated ISC has been identified as major fluorescence quenching channel, which becomes closed upon reaction with an amine explaining its fluorescence turn-on sensitivity.

Photochromism of 2-(2-Hydroxyphenyl) Benzothiazole (HBT) and Its Derivatives: A Theoretical Study.

Hydroxyphenyl benzothiazole (HBT), is a well-known organic system based on its special characteristic of the excited state hydrogen transfer (ESHT) following photoexcitation. However, the capability of this system regarding photochromism and photoswitching has not been addressed yet. In this study, we have investigated this issue by the aim of the MP2, CC2, ADC(2), and CASSCF theoretical methods. Also, we have considered several electron withdrawing groups and investigated their effects on the photophysical characteristics and spectroscopic properties of the enol and keto tautomers of the titled system. It has been predicted that the main HBT and its considered substitutions fulfill the essential characteristics required for photochromism. Also, substitution is an effective idea for tuning the photophysical nature of HBT and its similar systems. Our theoretical results verify that different substitutions alter the UV absorption of HBT systems from 330 to 351 nm and also the corresponding absorption wavelength of the γ-forms of 526-545 nm.

Direct observation of stepwise intermolecular proton and hydrogen transfer between alcohols and the triplet state of 4-nitro-1-naphthol.

Solvent assisted excited state intramolecular proton or hydrogen transfer has received much attention in bi-functional molecules with hydrogen donating and hydrogen accepting groups. As a typical photoacid, 1-naphthol exhibits photo-stable behavior in methanol; whether this would be disrupted by a bonded hydrogen accepting group contained in the molecule is still not assured. We present nanosecond transient absorption measurements relating to kinetics and the characteristic absorption of key intermediates upon the excitation of 4-nitro-1-naphthol in alcoholic solutions, and also transient resonance Raman spectroscopy studies combined with theoretical calculations to identify the structures of these intermediates, and we reveal the reaction mechanism to be stepwise deprotonation, hydrogen abstraction and protonation. These results demonstrate that alcohol assisted intramolecular proton or hydrogen transfer cannot occur in this system, but that the solvent cluster plays an important role during such stepwise reactions.

Dynamics of the excited-state hydrogen transfer in a (dG)·(dC) homopolymer: intrinsic photostability of DNA.

The intrinsic photostability of nucleic acids is intimately related to evolution of life, while its understanding at the molecular and electronic levels remains a challenge for modern science. Among the different decay pathways proposed in the last two decades, the excited-state hydrogen transfer between guanine-cytosine base pairs has been identified as an efficient non-reactive channel to dissipate the excess of energy provided by light absorption. The present work studies the dynamics of such phenomena taking place in a (dG)·(dC) B-DNA homopolymer in water solution using state-of-the-art molecular modelling and simulation methods. A dynamic effect that boosts the photostability of the inter-strand hydrogen atom transfers, inherent to the Watson-Crick base pairing, is unveiled and ascribed to the energy released during the proton transfer step. Our results also reveal a novel mechanism of DNA decay named four proton transfer (FPT), in which two protons of two adjacent G-C base pairs are transferred to form a biradical zwitterionic intermediate. Decay of the latter intermediate to the ground state triggers the transfer of the protons back to the guanine molecules recovering the Watson-Crick structure of the tetramer. This FPT process is activated by the close interaction of a nearby Na+ counterion with the oxygen atoms of the guanine nucleobases and hence represents a photostable channel operative in natural nucleic acids.

Electron-Proton Transfer Mechanism of Excited-State Hydrogen Transfer in Phenol-(NH3 )n (n=3 and 5).

Excited-state hydrogen transfer (ESHT) is responsible for various photochemical processes of aromatics, including photoprotection of nuclear basis. Its mechanism is explained by internal conversion from the aromatic ππ* to πσ* states via conical intersection. This means that the electron is transferred to a diffuse Rydberg-like σ* orbital apart from proton migration. This picture means the electron and the proton do not move together and the dynamics are different in principle. Here, we have applied picosecond time-resolved near-infrared (NIR) and infrared (IR) spectroscopy to the phenol-(NH3 )5 cluster, the benchmark system of ESHT, and monitored the electron transfer and proton motion independently. The electron transfer monitored by the NIR transition rises within 3 ps, while the overall H transfer detected by the IR absorption of NH vibration appears with a lifetime of about 20 ps. This clearly proves that the electron motion and proton migration are decoupled. Such a difference of the time-evolutions between the NIR absorption and the IR transition has not been detected in a cluster with three ammonia molecules. We will report our full observation together with theoretical calculations of the potential energy surfaces of the ππ* and πσ* states, and will discuss the ESHT mechanism and its cluster size-dependence between n=3 and 5. It is suggested that the presence and absence of a barrier in the proton transfer coordinate cause the different dynamics.

Fluorescence of tautomeric forms of curcumin in different pH and biosurfactant rhamnolipids systems: Application towards on-off ratiometric fluorescence temperature sensing

Medicinal properties of curcumin are widely getting realized. For its applicability as a hydrophobic drug molecule and food spice interaction of curcumin with rhamnolipids, a biosurfactant, bears importance. Here we have explored interaction of curcumin with rhamnolipids biosurfactant and its aggregation behavior. The impact of pH on critical micelle concentration (cmc) of rhamnolipids has been studied using fluorescence of curcumin and found that cmc of rhamnolipids increases with increase in pH of the medium. In acidic, neutral and slightly alkaline medium (pH8), at λex=355nm (for β-diketone form) curcumin undergoes excited state hydrogen transfer (ESHT) and emits solely from enol form both in the presence and absence of rhamnolipids, but first time we report that in extreme alkaline condition, at pH13, at λex=355nm curcumin emits from both β-diketone as well as enolic ESHT forms in absence of rhamnolipids but in the presence of rhamnolipids β-diketone is stabilized and the emission solely comes from β-diketone by completely revoking ESHT process. Fluorescence quenching by hydrophobic cetylpyridinium bromide confirms curcumin penetrates deep inside the hydrophobic pocket of rhamnolipid aggregates/micelle by reducing the distance between N+-atom of pyridinium ion and curcumin. On the other hand hydrophobic molecule like pyrene stays near to the Stern layer of rhamnolipids facilitating electron transfer from pyrene to N+-atom of pyridinium ion. Even in neutral condition, in the presence of rhamnolipids the β-diketone form, though in small proportions, can be stabilized in higher temperature in expense of enolic ESHT form, thus, offering an on off ratiometric fluorescence temperature sensing in solution, which bears significance as ratiometric probe molecules. Interaction of curcumin with rhamnolipids stabilizes curcumin in acidic, neutral and moderate alkaline condition but fails at extreme pH13.

Photochemistry of 1- and 2-Naphthols and Their Water Clusters: The Role of 1 ππ*(La ) Mediated Hydrogen Transfer to Carbon Atoms.

The computational analysis of the isomer- and conformer-dependent photochemistry of 1- and 2-naphthols and their microsolvated water clusters is motivated by their very different excited state reactivities. We present evidence that 1- and 2-naphthol follow distinct excited state deactivation pathways. The deactivation of 2-naphthols, 2-naphthol water clusters, as well as of the anti conformer of 1-naphthol is mediated by the optically dark 1 πσ* state. The dynamics of the 1 πσ* surface leads to the homolytic cleavage of the OH bond. On the contrary, the excited state deactivation of syn 1-naphthol and 1-naphthol water clusters follows an uncommon reaction pathway. Upon excitation to the bright 1 ππ*(La ) state, a highly specific excited state hydrogen transfer (ESHT) to carbon atoms C8 and C5 takes place, yielding 1,8- and 1,5-naphthoquinone methides. The ESHT pathway arises from the intrinsic electronic properties of the 1 ππ*(La ) state of 1-naphthols.

Non-typical fluorescence studies of excited and ground state proton and hydrogen transfer

Fluorescence studies of tautomerization have been carried out for various systems that exhibit single and double proton or hydrogen translocation in various environments, such as liquid and solid condensed phases, ultracold supersonic jets, and finally, polymer matrices with single emitters. We focus on less explored areas of application of fluorescence for tautomerization studies, using porphycene, a porphyrin isomer, as an example. Fluorescence anisotropy techniques allow investigations of self-exchange reactions, where the reactant and product are formally identical. Excitation with polarized light makes it possible to monitor tautomerization in single molecules and to detect their three-dimensional orientation. Analysis of fluorescence from single vibronic levels of jet-isolated porphycene not only demonstrates coherent tunneling of two internal protons, but also indicates that the process is vibrational mode-specific. Next, we present bifunctional proton donor-acceptor systems, molecules that are able, depending on the environment, to undergo excited state single intramolecular or double intermolecular proton transfer. For molecules that have donor and acceptor groups located in separate moieties linked by a single bond, excited state tautomerization can be coupled to mutual twisting of the two subunits.

Trapped Hydronium Radical Produced by Ultraviolet Excitation of Substituted Aromatic Molecule.

The gas phase structure and excited state dynamics of o-aminophenol-H2O complex have been investigated using REMPI, IR-UV hole-burning spectroscopy, and pump-probe experiments with picoseconds laser pulses. The IR-UV spectroscopy indicates that the isomer responsible for the excitation spectrum corresponds to an orientation of the OH bond away from the NH2 group. The water molecule acts as H-bond acceptor of the OH group of the chromophore. The complexation of o-aminophenol with one water molecule induced an enhancement in the excited state lifetime on the band origin. The variation of the excited state lifetime of the complex with the excess energy from 1.4 ± 0.1 ns for the 0-0 band to 0.24 ± 0.3 ns for the band at 0-0 + 120 cm(-1) is very similar to the variation observed in the phenol-NH3 system. This experimental result suggests that the excited state hydrogen transfer reaction is the dominant channel for the non radiative pathway. Indeed, excited state ab initio calculations demonstrate that H transfer leading to the formation of the H3O(•) radical within the complex is the main reactive pathway.

Electron-Proton Decoupling in Excited-State Hydrogen Atom Transfer in the Gas Phase.

Hydrogen-release by photoexcitation, excited-state-hydrogen-transfer (ESHT), is one of the important photochemical processes that occur in aromatic acids and is responsible for photoprotection of biomolecules. The mechanism is described by conversion of the initial state to a charge-separated state along the O(N)-H bond elongation, leading to dissociation. Thus ESHT is not a simple H-atom transfer in which a proton and a 1s electron move together. Here we show that the electron-transfer and the proton-motion are decoupled in gas-phase ESHT. We monitor electron and proton transfer independently by picosecond time-resolved near-infrared and infrared spectroscopy for isolated phenol-(ammonia)5 , a benchmark molecular cluster. Electron transfer from phenol to ammonia occurred in less than 3 picoseconds, while the overall H-atom transfer took 15 picoseconds. The observed electron-proton decoupling will allow for a deeper understanding and control of of photochemistry in biomolecules.

Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer.

The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH3)2 complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH3)2 cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocation analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A″((1)πσ*) and A'((1)nσ*) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A'((1)ππ*) and A″((1)nπ*) potential energy surfaces. For the unconstrained complex, potential energy profiles show two (1)ππ*-(1)πσ* conical intersections along enol → keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.

Analytic first derivatives of floating occupation molecular orbital-complete active space configuration interaction on graphical processing units

The floating occupation molecular orbital-complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the state-averaged complete active space self-consistent field (SA-CASSCF) method. We have formulated the analytic first derivative of FOMO-CASCI in a manner that is well-suited for a highly efficient implementation using graphical processing units (GPUs). Using this implementation, we demonstrate that FOMO-CASCI gradients are of similar computational expense to configuration interaction singles (CIS) or time-dependent density functional theory (TDDFT). In contrast to CIS and TDDFT, FOMO-CASCI can describe multireference character of the electronic wavefunction. We show that FOMO-CASCI compares very favorably to SA-CASSCF in its ability to describe molecular geometries and potential energy surfaces around minimum energy conical intersections. Finally, we apply FOMO-CASCI to the excited state hydrogen transfer reaction in methyl salicylate.