grebenshchikov_2007
===================

S\. Yu\. Grebenshchikov, Z\.\-W\. Qu, H\. Zhu and R\. Schinke, "New theoretical investigations of the photodissociation of ozone in the Hartley, Huggins, Chappuis, and Wulf bands", Phys\. Chem\. Chem\. Phys\. 9, 2044 \(2007\)

`Source record <https://github.com/LupoLab/optmat/blob/main/src/optmat/data/sources/grebenshchikov_2007.toml>`__ · :doc:`Catalogue </the-data/sources>` · :doc:`Review register </register>`

DOI: `10\.1039/b701020f <https://doi.org/10.1039/b701020f>`__

**Source kind:** theory

**Recorded technique:** A review of the authors' quantum\-dynamics studies of the four absorption bands of O3 \(200\-1100 nm\)\. Electronic structure\: MRCI with single and double excitations from state\-averaged full\-valence CASSCF \(18 electrons in 12 orbitals\), Davidson correction, aug\-cc\-pVTZ for the global surfaces \(cc\-pVQZ for 1 3A'\), MOLPRO; Table 1's thresholds, geometries, vertical energies and band origins from new aug\-cc\-pVQZ calculations made for the review \(pp\. 2045\-2047\)\. Wave\-packet dynamics on diabatic surfaces, surface hopping for the B/R crossing \(pp\. 2047\-2049\)\.

**Materials in structured entries:** O3

**Dataset quantities:** dissociation\_energy, transition\_dipole\_moment

**Contents:** 11 datasets; 0 formulas.

Curation notes
--------------

Identity checked on the first page \(PDF page 1 = journal p\. 2044\)\: Grebenshchikov, Qu, Zhu and Schinke, Phys\. Chem\. Chem\. Phys\. 9, 2044\-2064 \(2007\), a review \('Invited Article'\)\. PDF page n = journal page 2043 \+ n\. O3 only\.

PRODUCT CHANNELS \(eqns \(1\)\-\(5\), p\. 2045\)\: the photon energy above which each channel opens, 'the corresponding experimental threshold energies' \(Table 1 footnote b\), given without a reference\: 1\.051 eV O\(3P\) \+ O2\(X 3Sigma\_g\-\); 2\.026 eV O\(3P\) \+ O2\(a 1Delta\_g\); 2\.678 eV O\(3P\) \+ O2\(b 1Sigma\_g\+\); 3\.016 eV O\(1D\) \+ O2\(X 3Sigma\_g\-\); 3\.999 eV O\(1D\) \+ O2\(a 1Delta\_g\); and \(p\. 2062\) 4\.651 eV O\(1D\) \+ O2\(b 1Sigma\_g\+\)\. Inline datasets, use = check \(their origin is not cited\)\. Energies from O3\(X~\) in its ground vibrational state \(Fig\. 1 caption\: 'E = 0 corresponds to O3\(X~\) in the ground vibrational state'\), so D0\.

TABLE 1 \(p\. 2047; CSV, image checked, all cells agree\)\: the calculated D0 of channels \(1\), \(2\) and \(5\) \(1\.01, 2\.00, 3\.95 eV\), written; the transition dipole moments at the FC point, written\. Not written \(no quantity holds them as printed, or not asked\)\: the equilibrium bond lengths and angles, the harmonic\-like frequencies 'extracted from the calculated absorption cross sections' \(with references c\-j\), the vertical energies T\_v \(1\.561 1 3A', 1\.588 1 3A'', 1\.717 2 3A'', 1\.923 1 1A'', 1\.991 2 1A'', 4\.936 eV 3 1A'; with the X~ zero\-point energy 0\.176 eV 'taken into account'\), and the band origins T0 calculated \(1\.305, 1\.483, 1\.217, \-, 2\.086, 3\.44 eV\) and experimental \(1\.297, 1\.455, 1\.184, \-, 2\.059, 3\.361 eV, from refs\. 38, 20, 51, 20, 52\)\. The X~ equilibrium energy at this level is \-225\.20357642 hartree\.

QUANTUM YIELDS \(notes only\)\: in the Hartley band 'the observed quantum yield of this channel \[channel \(5\), O\(1D\) \+ O2\(a 1Delta\_g\)\] is as high as 85\-90 %' \(p\. 2049\) and 'About 10\-15 % of the products reach the triplet channel \(1\)' \(p\. 2050\), both citing Houston's review \(ref\. 13\: P\. L\. Houston, in Modern Trends in Chemical Reaction Dynamics, Part 2, World Scientific, 2005\)\. No wavelength is given and the values are ranges quoted from a review of other measurements\: not taken \(data rule 6\)\. The spin\-forbidden channels \(2\)\-\(4\) are 'very weakly populated' and seen in the Huggins band \(refs\. 14\-18, p\. 2045\)\.

Other figures of the paper, not taken\: the calculated Hartley absorption 'within 15 % of the experimental value' at the maximum \(p\. 2048\); the Chappuis calculation 'overestimates the absolute value near the maximum by 25 %' \(p\. 2057\); the isolated Wulf band 'only ~1\.4 x 10^\-22 cm^2 at the maximum' \(p\. 2059\); the Wulf \(0,0,0\) and 3B2 linewidths \(p\. 2061\)\.

Register\: TC\-973\.

**Recorded bibliographic identity status:** VALIDATED. This concerns identification of the source; it does not establish the scientific correctness of its contents.

Datasets
--------

grebenshchikov\_2007/d0\_channel\_1
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "d0_channel_1",
     "material": "O3",
     "file": "O3/grebenshchikov_2007__d0_channel_1.csv",
     "table": "tbl_6aebd02f5e84",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(3P) + O2(X 3Sigma_g-)"
     }
   }

Table 1 \(p\. 2047\), row D0, the channel '3P/3Sigma \(1\)' \(columns 1 1A' \(X~\), 1 3A', 1 3A'', 1 1A'', all 1\.01\)\: the calculated threshold of channel \(1\), MRCI\+Q/aug\-cc\-pVQZ\. The row label is the eqn number\. Against the experimental 1\.051 eV of eqn \(1\) \(exp\_channel\_1\)\. Uncertainty not stated\.

grebenshchikov\_2007/d0\_channel\_2
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "d0_channel_2",
     "material": "O3",
     "file": "O3/grebenshchikov_2007__d0_channel_2.csv",
     "table": "tbl_6aebd02f5e84",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(3P) + O2(a 1Delta_g)"
     }
   }

Table 1 \(p\. 2047\), row D0, the channel '3P/1Delta \(2\)' \(column 2 3A''\)\: 2\.00 eV, calculated\. Against the experimental 2\.026 eV of eqn \(2\)\.

grebenshchikov\_2007/d0\_channel\_5
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "d0_channel_5",
     "material": "O3",
     "file": "O3/grebenshchikov_2007__d0_channel_5.csv",
     "table": "tbl_6aebd02f5e84",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(1D) + O2(a 1Delta_g)"
     }
   }

Table 1 \(p\. 2047\), row D0, the channel '1D/1Delta \(5\)' \(columns 2 1A'', 3 1A'\)\: 3\.95 eV, calculated\. Against the experimental 3\.999 eV of eqn \(5\)\.

grebenshchikov\_2007/exp\_channel\_1
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_1",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(3P) + O2(X 3Sigma_g-)"
     }
   }

1 inline points in the source record.

Eqn \(1\), p\. 2045\: 'O3 \+ hbar omega \(E\_ph \> 1\.051 eV\) \-\> O\(3P\) \+ O2\(X 3Sigma\_g\-\)'; an experimental threshold \(Table 1 footnote b\) quoted without a reference\. Uncertainty not stated\.

grebenshchikov\_2007/exp\_channel\_2
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_2",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(3P) + O2(a 1Delta_g)"
     }
   }

1 inline points in the source record.

Eqn \(2\), p\. 2045\: E\_ph \> 2\.026 eV, O\(3P\) \+ O2\(a 1Delta\_g\); quoted without a reference\.

grebenshchikov\_2007/exp\_channel\_3
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_3",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(3P) + O2(b 1Sigma_g+)"
     }
   }

1 inline points in the source record.

Eqn \(3\), p\. 2045\: E\_ph \> 2\.678 eV, O\(3P\) \+ O2\(b 1Sigma\_g\+\); quoted without a reference\.

grebenshchikov\_2007/exp\_channel\_4
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_4",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(1D) + O2(X 3Sigma_g-)"
     }
   }

1 inline points in the source record.

Eqn \(4\), p\. 2045\: E\_ph \> 3\.016 eV, O\(1D\) \+ O2\(X 3Sigma\_g\-\); quoted without a reference\.

grebenshchikov\_2007/exp\_channel\_5
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_5",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(1D) + O2(a 1Delta_g)"
     }
   }

1 inline points in the source record.

Eqn \(5\), p\. 2045\: E\_ph \> 3\.999 eV, O\(1D\) \+ O2\(a 1Delta\_g\); quoted without a reference\.

grebenshchikov\_2007/exp\_channel\_6
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "exp_channel_6",
     "material": "O3",
     "table": "text",
     "quantity": "dissociation_energy",
     "unit": "eV",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "kind": "D0",
       "products": "O(1D) + O2(b 1Sigma_g+)"
     }
   }

1 inline points in the source record.

p\. 2062 \(Outlook\)\: 'the next higher singlet channel, O\(1D\) \+ O2\(b 1Sigma\_g\+\), with a threshold energy of 4\.651 eV', observed at 193 nm \(refs\. 114, 117, 118\); quoted without a reference for the energy\. Row '6' is not an eqn number of the paper\.

grebenshchikov\_2007/tdm
~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "tdm",
     "material": "O3",
     "file": "O3/grebenshchikov_2007__tdm.csv",
     "table": "tbl_6aebd02f5e84",
     "quantity": "transition_dipole_moment",
     "unit": "D",
     "abscissa": "label",
     "use": "check",
     "parameters": {
       "states": "the row label: the upper state <- X~ 1A' (1A1)",
       "geometry": "the Franck-Condon point (the X~ equilibrium of Table 1: R1 = R2 = 2.409 a0, alpha = 116.9 deg)"
     }
   }

Table 1 \(p\. 2047\), row mu, footnote o\: the moments from X~ to the triplets 1 3A' \(3B2\), 1 3A'' \(3B1\), 2 3A'' \(3A2\), 'calculated as described in Section VI' \(spin\-orbit\-induced, MRCI, p\. 2059\), and 0 for 1 1A'' \(1A2\), dipole\-forbidden at the C2v FC point\. Rows labelled by the C\_s state\. The Wulf calculation fixes the moments at these FC values \(p\. 2059\)\. Uncertainty not stated\.

grebenshchikov\_2007/tdm\_earlier
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

.. code-block:: text

   {
     "id": "tdm_earlier",
     "material": "O3",
     "file": "O3/grebenshchikov_2007__tdm_earlier.csv",
     "table": "tbl_6aebd02f5e84",
     "quantity": "transition_dipole_moment",
     "unit": "D",
     "abscissa": "label",
     "use": "reproduced",
     "reproduced_from": [
       "Z.-W. Qu, H. Zhu, S. Yu. Grebenshchikov, R. Schinke and S. C. Farantos, J. Chem. Phys. 121, 11731 (2004)",
       "S. Yu. Grebenshchikov, R. Schinke, Z.-W. Qu and H. Zhu, J. Chem. Phys. 124, 204313 (2006)"
     ],
     "parameters": {
       "states": "the row label: the upper state <- X~ 1A' (1A1)",
       "geometry": "the Franck-Condon point (the X~ equilibrium)"
     }
   }

Table 1 \(p\. 2047\), row mu, footnote o\: 'those for 2 1A'' and 3 1A' are taken from ref\. 43 and 49, respectively' \(0\.06 D Chappuis, 2\.13 D Hartley/Huggins\)\. The table's own frequency footnotes attach ref\. 49 to 2 1A'' \(the Chappuis state\) and ref\. 43 to 3 1A' \(the Huggins band, Section IV\), so 'respectively' is probably reversed; both references are kept\.

Formulas
--------

No formulas are recorded.

Corrections
-----------

No dataset errata are recorded in this source record.

Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the :doc:`review register </register>` for the checks and decisions.