Automerization Of Cyclobutadiene Research Articles

Performance Tests of the Second-Order Approximate Internally Contracted Multireference Coupled-Cluster Singles and Doubles Method icMRCC2.

Benchmark results are presented for the second-order approximation of the internally contracted multireference coupled-cluster method with single and double excitations, icMRCC2 [Köhn, Bargholz, J. Chem. Phys. 2019, 151, 041106], which was designed as a multireference analogue of the single-reference second-order approximate coupled-cluster method CC2 [Christiansen, Koch, Jørgensen, Chem. Phys. Lett. 1995, 243, 409-418]. Vertical excitation energies of various small to medium-sized organic molecules are investigated based on established test sets from the literature. Additionally, the spectroscopic constants of ground and excited states of diatomics and the geometric parameters of excited triatomic molecules were determined and compared to the experimental data. The results show that the method clearly extends the applicability of single-reference CC2, including doubly excited states, and also artifacts of CC2 like too low Rydberg excitations and too weak multiple bonds are eliminated. The method is computationally more demanding than standard multireference second-order perturbation theories but improves significantly in accuracy, as shown by the benchmark results. In addition, it is demonstrated that small active spaces are often sufficient to obtain accurate energies with icMRCC2. Example applications like the automerization of cyclobutadiene, the deactivation pathway of ethylene, and the excited states of an iron complex with a noninnocent nitrosyl ligand demonstrate the potential of icMRCC2 in cases with strong multireference character.

Spin-Flip Unitary Coupled Cluster Method: Toward Accurate Description of Strong Electron Correlation on Quantum Computers.

Quantum computers have emerged as a promising platform to simulate strong electron correlation that is crucial to catalysis and photochemistry. However, owing to the choice of a trial wave function employed in the variational quantum eigensolver (VQE) algorithm, accurate simulation is restricted to certain classes of correlated phenomena. Herein, we combine the spin-flip (SF) formalism with the unitary coupled cluster with singles and doubles (UCCSD) method via the quantum equation-of-motion (qEOM) approach to allow for an efficient simulation of a large family of strongly correlated problems. We show that the developed qEOM-SF-UCCSD/VQE method outperforms its UCCSD/VQE counterpart for simulation of the cis-trans isomerization of ethylene, and the automerization of cyclobutadiene and the predicted qEOM-SF-UCCSD/VQE barrier heights are in a good agreement with the experimentally determined values. The developments presented herein will further stimulate the investigation of this approach for simulations of other types of correlated/entangled phenomena on quantum computers.

High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction.

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017) and J. E. Deustua, J. Shen, and P. Piecuch, J. Chem. Phys. 154, 124103 (2021)], we propose a novel form of the CC(P; Q) theory in which the stochastic Quantum Monte Carlo propagations, used to identify dominant higher-than-doubly excited determinants, are replaced by the selected configuration interaction (CI) approach using the perturbative selection made iteratively (CIPSI) algorithm. The advantages of the resulting CIPSI-driven CC(P; Q) methodology are illustrated by a few molecular examples, including the dissociation of F2 and the automerization of cyclobutadiene, where we recover the electronic energies corresponding to the CC calculations with a full treatment of singles, doubles, and triples based on the information extracted from compact CI wave functions originating from relatively inexpensive Hamiltonian diagonalizations.

High-level coupled-cluster energetics by Monte Carlo sampling and moment expansions: Further details and comparisons.

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC(P;Q) formalism with the stochastic configuration interaction (CI) and CC Quantum Monte Carlo (QMC) propagations. This article extends our initial study [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)], which focused on recovering the energies obtained with the CC method with singles, doubles, and triples (CCSDT) using the information extracted from full CI QMC and CCSDT-MC, to the CIQMC approaches truncated at triples and quadruples. It also reports our first semi-stochastic CC(P;Q) calculations aimed at converging the energies that correspond to the CC method with singles, doubles, triples, and quadruples (CCSDTQ). The ability of the semi-stochastic CC(P;Q) formalism to recover the CCSDT and CCSDTQ energies, even when electronic quasi-degeneracies and triply and quadruply excited clusters become substantial, is illustrated by a few numerical examples, including the F-F bond breaking in F2, the automerization of cyclobutadiene, and the double dissociation of the water molecule.

Fully variational incremental CASSCF.

The complete-active-space self-consistent field (CASSCF) method is a canonical electronic structure theory that holds a central place in conceptualizing and practicing first principles simulations. For application to realistic molecules, however, the CASSCF must be approximated to circumvent its exponentially scaling computational costs. Applying the many-body expansion-also known as the method of increments-to CASSCF (iCASSCF) has been shown to produce a polynomially scaling method that retains much of the accuracy of the parent theory and is capable of treating full valence active spaces. Due to an approximation made in the orbital gradient, the orbital parameters of the original iCASSCF formulation could not be variationally optimized, which limited the accuracy of its nuclear gradient. Herein, a variational iCASSCF is introduced and implemented, where all parameters are fully optimized during energy minimization. This method is able to recover electronic correlations from the full valence space in large systems, produce accurate gradients, and optimize stable geometries as well as transition states. Demonstrations on challenging test cases, such as the oxoMn(salen)Cl complex with 84 electrons in 84 orbitals and the automerization of cyclobutadiene, show that the fully variational iCASSCF is a powerful tool for describing challenging molecular chemistries.

Quantum mechanical tunneling in the automerization of cyclobutadiene.

Cyclobutadiene has a four-membered carbon ring with two double bonds, but this highly strained molecular configuration is almost square and, via a coordinated motion, the nuclei quantum mechanically tunnels through the high-energy square state to a configuration equivalent to the initial configuration under a 90° rotation. This results in a square ground state, comprising a superposition of two molecular configurations, that is driven by quantum tunneling. Using a quantum mechanical model, and an effective nuclear potential from density functional theory, we calculate the vibrational energy spectrum and the accompanying wavefunctions. We use the wavefunctions to identify the motions of the molecule and detail how different motions can enhance or suppress the tunneling rate. This is relevant for kinematics of tunneling-driven reactions, and we discuss these implications. We are also able to provide a qualitative account of how the molecule will respond to an external perturbation and how this may enhance or suppress infra-red-active vibrational transitions.

W3X: A Cost-Effective Post-CCSD(T) Composite Procedure.

We have formulated the W3X procedure by incorporating cost-effective post-CCSD(T) components (up to the CCSDT(Q) level) into the W1X-1 protocol, the latter representing a recently reported economical yet accurate approximation to CCSD(T)/CBS. For medium-sized systems, W3X is moderately more computationally demanding than W1X-1, but it is significantly less costly than the W3.2lite and (especially) W3.2 procedures. Because of the use of the cost-effective W1X-1 method as the underlying CCSD(T) component, W3X is also less expensive than the W2.2 protocol, which does not incorporate post-CCSD(T) excitations. We find that, for single-reference systems (the G2/97 set and most of the W4-11 set), W3X is comparable in accuracy to the underlying W1X-1 protocol, as might have been expected. For the more challenging cases of the multireference systems within the W4-11 set, the dissociation of F2 and the automerization of cyclobutadiene, W3X provides improved performance compared with the CCSD(T)-based procedures (W1X-1 and W2.2). Highly multireference chromium oxides CrO, CrO2, and CrO3 are still somewhat challenging for W3X (and even for the higher-level W3.2lite and W3.2 procedures), but the inclusion of the economical post-CCSD(T) terms in W3X already leads to a significant improvement over W1X-1. Thus, W3X provides a cost-effective means for treating systems with significant (but perhaps not excessive) multireference character that are otherwise not well-described by CCSD(T)-based methods.

Empirical Correction of Nondynamical Correlation Energy for Density Functionals

To provide an efficient means to address nondynamical correlation, an empirical correction for single and double hybrid density functionals has been formulated. The correction utilizes the highest doubly occupied, lowest unoccupied, and singly occupied generalized Kohn-Sham orbitals and, for potential energy curves, a few additional strongly correlated orbitals. Utilizing proposed nondynamical correlation corrections, hybrid BLYP predicted potential energy curves that fit well to those obtained by ab initio multireference methods for the torsional rotation of ethylene and the automerization of cyclobutadiene. The empirical nondynamical correlation corrections, calculated at the transition structures, also reduce the overall errors of B2K-PLYP for the DBH24 and BH76 barrier height data sets. The proposed empirical correction can efficiently enhance the utility of both single and double hybrid density functionals for chemical situations with moderate to significant nondynamical correlation.

Inactive excitations in Mukherjee's state-specific multireference coupled cluster theory treated with internal contraction: Development and applications

One generic difficulty of most state-specific many-body formalisms using the Jeziorski-Monkhorst ansatz: ψ = Σ(μ)exp(T(μ))|φ(μ)>c(μ) for the wave-operators is the large number of redundant cluster amplitudes. The number of cluster amplitudes up to a given rank is many more in number compared to the dimension of the Hilbert Space spanned by the virtual functions of up to the same rank of excitations. At the same time, all inactive excitations--though linearly independent--are far too numerous. It is well known from the success of the contracted multi-reference configuration interaction (MRCI(SD)) that, at least for the inactive double excitations, their model space dependence (μ-dependence) is weak. Considerable simplifications can thus be obtained by using a partially internally contracted description, which uses the physically appealing approximation of taking the inactive excitations T(i) to be independent of the model space labels (μ-independent). We propose and implement in this paper such a formalism with internal contractions for inactive excitations (ICI) within Mukherjee's state-specific multi-reference coupled cluster theory (SS-MRCC) framework (referred to from now on as the ICI-SS-MRCC). To the extent the μ-independence of T(i) is valid, we expect the ICI-SS-MRCC to retain the conceptual advantages of size-extensivity yet using a drastically reduced number of cluster amplitudes without sacrificing accuracy. Moreover, greater coupling is achieved between the virtual functions reached by inactive excitations as a result of the internal contraction while retaining the original coupling term for the μ-dependent excitations akin to the parent theory. Another major advantage of the ICI-SS-MRCC, unlike the other analogous internally contracted theories, such as IC-MRCISD, CASPT2, or MRMP2, is that it can use relaxed coefficients for the model functions. However, at the same time it employs projection manifolds for the virtuals obtained from inactive n hole-n particle (nh-np) excitations on the entire reference function containing relaxed model space coefficients. The performance of the method has been assessed by applying it to compute the potential energy surfaces of the prototypical H(4); to the torsional potential energy barrier for the cis-trans isomerism in C(2)H(4) as well as that of N(2)H(2), automerization of cyclobutadiene, single point energy calculation of CH(2), SiH(2), and comparing them against the SS-MRCC results, benchmark full CI results, wherever available and those from the allied MR formalisms. Our findings are very much reminiscent of the experience gained from the IC-MRCISD method.

Tetra-radical and ionic S 1/S 0 conical intersections of cyclobutadiene

We have located two conical intersections between the first singlet excited (S 1) and singlet ground (S 0) states of cyclobutadiene (CBD) using the complete active space self-consistent field (CASSCF) method. One is the ionic-structure S 1/S 0 conical intersection (CI ionic), which was located by carrying out a minimum-energy-path calculation from the Franck–Condon point of the HOMO to LUMO double-electron excited state, and the other is the tetra-radical S 1/S 0 conical intersection (CI tetra), which was located by exploring the S 1/S 0 degeneracy space. While CI ionic is only involved in the automerization of CBD, CI tetra is involved in not only the automerization but also the criss–cross reaction. It is possible for one of the highest constrained compounds, tetrahedrane, to be produced if S 1 excited CBD undergoes a transition to the S 0 state via the tetra-radical S 1/S 0 conical intersection. In this paper, we discuss the possibility that unsubstituted tetrahedrane can be produced by irradiating CBD.

Accounting for the exact degeneracy and quasidegeneracy in the automerization of cyclobutadiene via multireference coupled-cluster methods

The automerization of cyclobutadiene (CBD) is employed to test the performance of the reduced multireference (RMR) coupled-cluster (CC) method with singles and doubles (RMR CCSD) that employs a modest-size MR CISD wave function as an external source for the most important (primary) triples and quadruples in order to account for the nondynamic correlation effects in the presence of quasidegeneracy, as well as of its perturbatively corrected version accounting for the remaining (secondary) triples [RMR CCSD(T)]. The experimental results are compared with those obtained by the standard CCSD and CCSD(T) methods, by the state universal (SU) MR CCSD and its state selective or state specific (SS) version as formulated by Mukherjee et al. (SS MRCC or MkMRCC) and, wherever available, by the Brillouin-Wigner MRCC [MR BWCCSD(T)] method. Both restricted Hartree-Fock (RHF) and multiconfigurational self-consistent field (MCSCF) molecular orbitals are employed. For a smaller STO-3G basis set we also make a comparison with the exact full configuration interaction (FCI) results. Both fundamental vibrational energies-as obtained via the integral averaging method (IAM) that can handle anomalous potentials and automatically accounts for anharmonicity- and the CBD automerization barrier for the interconversion of the two rectangular structures are considered. It is shown that the RMR CCSD(T) potential has the smallest nonparallelism error relative to the FCI potential and the corresponding fundamental vibrational frequencies compare reasonably well with the experimental ones and are very close to those recently obtained by other authors. The effect of anharmonicity is assessed using the second-order perturbation theory (MP2). Finally, the invariance of the RMR CC methods with respect to orbital rotations is also examined.

Application of Double Ionization State-Specific Equation of Motion Coupled Cluster Method to Organic Diradicals

The state-specific equation of motion coupled cluster method is applied to three systems of diradical character: automerization of cyclobutadiene, singlet-triplet gaps of trimethylmethylene, and Bergman reaction. The aim of the paper is to assess the performance of the method and test numerically the importance of orbital optimization, three-body terms in transformed Hamiltonian, and the choice of cluster equations.

Multireference coupled-cluster calculations on the energy of activation in the automerization of cyclobutadiene: Assessment of the state-specific multireference Brillouin–Wigner theory

Hilbert-space state-universal multireference coupled-cluster (MR CC) data on cyclobutadiene [A. Balková and R. J. Bartlett, J. Chem. Phys. 101, 8972 (1994)] were used as a benchmark for testing our recently developed state-specific (single-root) multireference Brillouin-Wigner coupled-cluster (MR BWCC) theory. For the energy of activation in the automerization of cyclobutadiene (i.e., the energy difference between the square and rectangular structures) at the CCSD/[3s2p1d/2s] level of theory, our MR BWCCSD method gives the value of 6.2 kcal/mol, compared to 6.5 kcal/mol given by MR CCSD. With the cc-pVDZ and cc-pVTZ/cc-pVDZ basis sets, the MR BWCCSD activation barrier is 6.4 and 7.0 kcal/mol, respectively. The effect of the triple excitations [in MR CCSD(T)] and of the frozen core approximation were estimated previously to be below 0.1 kcal/mol and in the opposite direction. This shows the way of how to arrive at a more accurate automerization barrier in future calculations: extension of the basis set seems to be more important than going beyond the CCSD(T) or MB BWCCSD level of the theory.

A comparison between DFT and other ab initio schemes on the activation energy in the automerization of cyclobutadiene

The influence of the multireference character in the transition state for the automerization reaction of cyclobutadiene is considered. We have analyzed two forms of taking into account this effect: either by the use of two-body density functionals or traditional density functional theory (DFT) correlation functionals conveniently modified. Comparison has also been made with conventional density functional theory Kohn–Sham (DFT–KS) [15]approaches. It is shown that only when the aforementioned multideterminantal character is included in the computational scheme is the activation energy in accord with accurate benchmark calculations.

Tunneling effects in the NMR spectrum of a spin in a symmetrical double-well potential

It has recently been suggested that tunneling may provide a mechanism for the automerization of cyclobutadiene and for other bond-shift reactions (I-3). Tunneling frequencies can be large even for rearrangements involving heavy atoms if the energy minima have very small separations. Since 13C NMR at low temperatures is used to investigate such systems (4), it is of interest to consider how tunneling, if present, would affect the spectra. NMR spectra have previously been calculated for tunneling protons in methyl groups and in tetrahedral molecules with strong dipole-dipole interactions (5-7). The much simpler problem of tunneling effects in MAS/CP spectra of 13C nuclei has apparently not been addressed. It is the purpose of this note to present NMR spectra for a spin-4 particle in a symmetric double-well potential where the spin Hamiltonian only includes chemical-shift terms. This would be a reasonable model for a ’ 3C nucleus in the norbornyl cation if a double-well potential were present (3). The calculation would not be changed in any way if two r3C nuclei interchanged their chemical shifts in the rearrangement reaction, and this would ensure that the double-well potential was in fact symmetrical; i.e., there would be no isotopic perturbation (8). In the spirit of a two-site exchange problem the Hamiltonian in frequency units (hertz) is taken to have the form

Tunneling in the automerization of cyclobutadiene

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTunneling in the automerization of cyclobutadieneMing Ju Huang and Max WolfsbergCite this: J. Am. Chem. Soc. 1984, 106, 14, 4039–4040Publication Date (Print):July 1, 1984Publication History Published online1 May 2002Published inissue 1 July 1984https://doi.org/10.1021/ja00326a029RIGHTS & PERMISSIONSArticle Views192Altmetric-Citations40LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (322 KB) Get e-Alerts Get e-Alerts