skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 10:00 PM to 12:00 PM ET on Tuesday, March 25 due to maintenance. We apologize for the inconvenience.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Studying excited-state-specific perturbation theory on the Thiel set
We explore the performance of a recently introduced N5-scaling excited-state-specific second order perturbation theory (ESMP2) on the singlet excitations of the Thiel benchmarking set. We find that, without regularization, ESMP2 is quite sensitive to π system size, performing well in molecules with small π systems but poorly in those with larger π systems. With regularization, ESMP2 is far less sensitive to π system size and shows a higher overall accuracy on the Thiel set than CC2, equation of motion-coupled cluster with singles and doubles, CC3, and a wide variety of time-dependent density functional approaches. Unsurprisingly, even regularized ESMP2 is less accurate than multi-reference perturbation theory on this test set, which can, in part, be explained by the set’s inclusion of some doubly excited states but none of the strong charge transfer states that often pose challenges for state-averaging. Beyond energetics, we find that the ESMP2 doubles norm offers a relatively low-cost way to test for doubly excited character without the need to define an active space.  more » « less
Award ID(s):
1848012
PAR ID:
10517624
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
The Journal of Chemical Physics
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
158
Issue:
22
ISSN:
0021-9606
Page Range / eLocation ID:
224113
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, The Journal of Chemical Physics)
    The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is capable of computing reliable energies, wave functions, and first-order properties of excited states in diradicals and polyenes that have a significant doubly excited character with respect to the ground state, without the need for including the computationally expensive triple excitations. Here, we extend the capabilities of the EOM-DEA-CCSD method to the calculations of a multiphoton property, two-photon absorption (2PA) cross sections. Closed-form expressions for the 2PA cross sections are derived within the expectation-value approach using response wave functions. We analyze the performance of this new implementation by comparing the EOM-DEA-CCSD energies and 2PA cross sections with those computed using the CC3 quadratic response theory approach. As benchmark systems, we consider transitions to the states with doubly excited character in twisted ethene and in polyenes, for which EOM-EE-CCSD (EOM-CCSD for excitation energies) performs poorly. The EOM-DEA-CCSD 2PA cross sections are comparable with the CC3 results for twisted ethene; however, the discrepancies between the two methods are large for hexatriene. The observed trends are explained by configurational analysis of the 2PA channels. 
    more » « less
  2. ; ; ; ; ; ; (, The Journal of Chemical Physics)
    We report the experimental resonance enhanced multiphoton ionization spectrum of isoquinoline between 315 and 310 nm, along with correlated electronic structure calculations on the ground and excited states of this species. This spectral region spans the origin transitions to a π–π* excited state, which previous work has suggested to be vibronically coupled with a lower lying singlet n–π* state. Our computational results corroborate previous density functional theory calculations that predict the vertical excitation energy for the n–π* state to be higher than the π–π* state; however, we find an increase in the C–N–C angle brings the n–π* state below the energy of the π–π* state. The calculations find two out-of-plane vibrational modes of the n–π* state, which may be brought into near resonance with the π–π* state as the C–N–C bond angle increases. Therefore, the C–N–C bond angle may be important in activating vibronic coupling between the states. We fit the experimental rotational contour with a genetic algorithm to determine the excited state rotational constants and orientation of the transition dipole moment. The fits show a mostly in-plane polarized transition, and the projection of the transition dipole moment in the a-b plane is about 84° away from the a axis. These results are consistent with the prediction of our electronic structure calculations for the transition dipole moment of the π–π* excited state. 
    more » « less
  3. ; ; (, Physical Chemistry Chemical Physics)
    The strong couplings between electronic states in conical intersection regions are among the most challenging problems in quantum chemistry. XMS-CASPT2, a second-order multireference quasidegenerate perturbation theory, has been successful in describing potential energy surfaces near the conical intersections. We have recently proposed a less expensive method for this problem, namely state-interaction pair-density functional theory (SI-PDFT), which considers the coupling between electronic states described by multiconfiguration pair-density functional theory (MC-PDFT). Here we test the accuracy of SI-PDFT for closely coupled potential energy surfaces of methylamine along five different reaction paths for N–H bond fission. We choose paths that pass close to a conical intersection of the ground and first excited states. We find that SI-PDFT predicts potential energy curves and energy splittings near the locally avoided crossing in close proximity to those obtained by XMS-CASPT2. This validates the method for application to photochemical simulations. 
    more » « less
  4. ; ; ; ; ; (, The Journal of Physical Chemistry A)
    The nonplanar character of graphene with a single carbon vacancy defect (SV) is investigated utilizing a pyrene-SV model system by way of complete active space self-consistent field theory (CASSCF) and multi-reference configuration interaction singles and doubles (MRCISD) calculations. Planar structures were optimized with both methods showing the 3B1 state as the ground state with three energetically close states within an energy range of 1 eV. These planar structures constitute saddle-points. However, upon following the out-of-plane imaginary frequency yields more stable (by 0.22 to 0.53 eV), but non-planar structures of CS symmetry. Of these, the 1A’ structure is the lowest in energy and is strongly deformed into an L-shape. Following a further out-of-plane imaginary frequency in the non-planar structures leads to the most stable, but most deformed singlet structure of C1 symmetry. In this structure a bond is formed between the carbon atom with the dangling bond and a carbon of the cyclopentadienyl ring. This bond stabilizes the structure by more than 3 eV compared to the planar 3B1 structure. Higher excited states were calculated at MR-CISD level showing a grouping of four states low in energy and higher states starting around 3 eV. 
    more » « less
  5. ; ; (, The Astrophysical Journal)
    Abstract Integral field spectroscopy of high-redshift galaxies has become a powerful tool for understanding their dynamics and evolutionary states. However, in the case of gravitationally lensed systems, it has proved difficult to model both lensing and intrinsic kinematics in a way that takes full advantage of the information available in the spectral domain. In this paper, we introduce a new method for pixel-based source reconstruction that alters standard regularization schemes for two-dimensional (2D) data in a way that leverages kinematic information in a physically motivated but flexible fashion, and that is better suited to the three-dimensional (3D) nature of integral field data. To evaluate the performance of this method, we compare its results to those of a more traditional 2D nonparametric approach using mock Atacama Large Millimeter/submillimeter Array (ALMA) observations of a typical high-redshift dusty star-forming galaxy. We find that 3D regularization applied to an entire data cube reconstructs a source’s intensity and velocity structure more accurately than 2D regularization applied to separate velocity channels. Cubes reconstructed with 3D regularization also have more uniform noise and resolution properties and are less sensitive to the signal-to-noise ratio of individual velocity channels than the results of 2D regularization. Our new approach to modeling integral field observations of lensed systems can be implemented without making restrictive a priori assumptions about intrinsic kinematics, and opens the door to new observing strategies that prioritize spectral resolution over spatial resolution (e.g., for multiconfiguration arrays like ALMA). 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email