(It's not strictly CI, but the implementation of time-dependent HF or RPA is essentially the same for TDDFT or Tamm-Dancoff Approximation TDDFT.)
Anyway, since you're performing a calculation on an open-shell system, the formulation for the state will include all one-electron excitations AND all one-electron de-excitations. That state has a de-excitation from 454B into 453B (i.e., the SOMO will fill the hole left by the excitation). Now you may think "but that doesn't accomplish anything." Remember that Gaussian only prints the dominant coefficients.
For this reason, Rich Martin created the Natural Transition Orbitals method as a nice way to express the excitation, rather than a set of coefficients and the ground-state orbitals.
Oftentimes, there is no dominant configuration in the list of excitation amplitudes, thereby making a straightforward interpretation of the excited state difficult. This is particularly unsatisfactory when attempting to determine the qualitative nature of an excited state. An additional complication in the DFT case is that in principle all orbitals in DFT but the HOMO are devoid of physical significance. However, chemical intuition is built on the orbital construct, and a simple orbital interpretation of "what got excited to where" is important.
This is available in Gaussian from the Population keyword and in other codes.
(It's not strictly CI, but the implementation of time-dependent HF or RPA is essentially the same for TDDFT or Tamm-Dancoff Approximation TDDFT.)
Anyway, since you're performing a calculation on an open-shell system, the formulation for the state will include all one-electron excitations AND all one-electron de-excitations. That state has a de-excitation from 454B into 453B (i.e., the SOMO will fill the hole left by the excitation). Now you may think "but that doesn't accomplish anything." Remember that Gaussian only prints the dominant coefficients.
For this reason, Rich Martin created the Natural Transition Orbitals method as a nice way to express the excitation, rather than a set of coefficients and the ground-state orbitals.
Oftentimes, there is no dominant configuration in the list of excitation amplitudes, thereby making a straightforward interpretation of the excited state difficult. This is particularly unsatisfactory when attempting to determine the qualitative nature of an excited state. An additional complication in the DFT case is that in principle all orbitals in DFT but the HOMO are devoid of physical significance. However, chemical intuition is built on the orbital construct, and a simple orbital interpretation of "what got excited to where" is important.
This is available in Gaussian from the Population keyword and in other codes.
I spent almost the week reading about RPA here and there, and as far as I understand your are right: "de-excitations" (as well as "excitations") are involved in the wave function expansion in RPA. And I simply did not know that.More
Time-dependent DFT can be used to predict excitation energies through a linear-response formulation.
In this Gaussian result, beyond the first line, you are looking at the largest coefficients in the configuration-interaction (CI) style expansion.
(It's not strictly CI, but the implementation of time-dependent HF or RPA is essentially the same for TDDFT or Tamm-Dancoff Approximation TDDFT.)
Anyway, since you're performing a calculation on an open-shell system, the formulation for the state will include all one-electron excitations AND all one-electron de-excitations. That state has a de-excitation from 454B into 453B (i.e., the SOMO will fill the hole left by the excitation). Now you may think "but that doesn't accomplish anything." Remember that Gaussian only prints the dominant coefficients.
For this reason, Rich Martin created the Natural Transition Orbitals method as a nice way to express the excitation, rather than a set of coefficients and the ground-state orbitals.
This is available in Gaussian from the Population keyword and in other codes.
Incidentally, there's a nice review of TDDFT in: "Progress in Time-Dependent Density-Functional Theory" Annual Review of Physical Chemistry Vol. 63: 287-323.
Time-dependent DFT can be used to predict excitation energies through a linear-response formulation.
In this Gaussian result, beyond the first line, you are looking at the largest coefficients in the configuration-interaction (CI) style expansion.
(It's not strictly CI, but the implementation of time-dependent HF or RPA is essentially the same for TDDFT or Tamm-Dancoff Approximation TDDFT.)
Anyway, since you're performing a calculation on an open-shell system, the formulation for the state will include all one-electron excitations AND all one-electron de-excitations. That state has a de-excitation from 454B into 453B (i.e., the SOMO will fill the hole left by the excitation). Now you may think "but that doesn't accomplish anything." Remember that Gaussian only prints the dominant coefficients.
For this reason, Rich Martin created the Natural Transition Orbitals method as a nice way to express the excitation, rather than a set of coefficients and the ground-state orbitals.
This is available in Gaussian from the Population keyword and in other codes.
Incidentally, there's a nice review of TDDFT in: "Progress in Time-Dependent Density-Functional Theory" Annual Review of Physical ChemistryVol. 63: 287-323.
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