4.2.38. MULA ¤

Warning

This program is not available in OpenMolcas

The MULA calculates intensities of vibrational transitions between electronic states.

4.2.38.1. Dependencies

The MULA program may need one or more UNSYM files produced by the MCLR program, depending on input options.

4.2.38.2. Files

4.2.38.2.1. Input files

UNSYM

Output file from the MCLR program.

4.2.38.2.2. Output files

plot.intensity

Contains data for plotting an artificial spectrum.

4.2.38.3. Input

The input for MULA begins after the program name:

&MULA

There are no compulsory keyword.

4.2.38.3.1. Keywords

TITLe

Followed by a single line, the title of the calculation.

FORCe

A force field will be given as input (or read from file), defining two oscillators for which individual vibrational levels and transition data will be computed.

ATOMs

Followed by one line for each individual atom in the molecule. On each line is the label of the atom, consisting of an element symbol followed by a number. After the label, separated by one or more blanks, one can optionally give a mass number; else, a standard mass taken from the file data/atomic.data. After these lines is one single line with the keyword “END of atoms”.

INTErnal

Specification of which internal coordinates that are to be used in the calculation. Each subsequent line has the form “BOND a b” or “ANGLE a b c” or or “TORSION a b c d” or or “OUTOFPL a b c d”, for bond distances, valence angles, torsions (e.g. dihedral angles), and out-of-plane angles. Here, ad stand for atom labels. After these lines follows one line with the keyword “END of internal”.

MODEs

Selection of modes to be used in the intensity calculation. This is followed by a list of numbers, enumerating the vibrational modes to use. The modes are numbered sequentially in order of vibrational frequency. After this list follows one line with the keyword “END of modes”.

MXLEvels

Followed by one line with the maximum number of excitations in each of the two states.

VARIational

If this keyword is included, a variational calculation will be made, instead of using the default double harmonic approximation.

TRANsitions

Indicates the excitations to be printed in the output. Followed by the word FIRST on one line, then a list of numbers which are the number of phonons — the excitation level — to be distributed among the modes, defining the vibrational states of the first potential function (force field). Then similarly, after a line with the word SECOND, a list of excitation levels for the second state.

ENERgies

The electronic \(T_0\) energies of the two states, each value is followed by either “eV” or “au”.

GEOMetry

Geometry input. Followed by keywords FILE, CARTESIAN, or INTERNAL. If FILE, the geometry input is taken from UNSYM1 and UNSYM2. If CARTESIAN or INTERNAL, two sections follow, one headed by a line with the word FIRST, the other with the word SECOND. For the CARTESIAN case, the following lines list the atoms and coordinates. On each line is an atom label, and the three coordinates (\(x,y,z\)). For the INTERNAL case, each line defines an internal coordinate in the same way as for keyword INTERNAL, and the value.

MXORder

Maximum order of transition dipole expansion. Next line is 0, if the transition dipole is constant, 1 if it is a linear function, etc.

OSCStr

If this keyword is included, the oscillator strength, instead of the intensity, of the transitions will calculated.

BROAdplot

Gives the peaks in the spectrum plot an artificial halfwidth. The default lifetime is \(130\cdot 10^{-15}\) s but this can be changed with keyword LIFEtime followd by the value.

NANOmeters

If this keyword is included, the plot file will be in nanometers. Default is in eV.

CM-1

If this keyword is included, the plot file will be in cm\(^{-1}\). Default is in eV.

PLOT

Enter the limits (in eV, cm\(^{-1}\), or in nm) for the plot file.

VIBWrite

If this keyword is included, the vibrational levels of the two states will be printed in the output.

VIBPlot

Two files, plot.modes1 and plot.modes2, will be generated, with pictures of the normal vibrational modes of the two electronic states.

HUGElog

This keyword will give a much more detailed output file.

SCALe

Scales the Hessians, by multiplying with the scale factors following this keyword.

DIPOles

Transition dipole data. If MXORDER=0 (see above), there follows a single line with \(x,y,z\) components of the transition dipole moment. If MXORDER=1 there are an additional line for each cartesian coordinate of each atom, with the derivative of the transition dipole moment w.r.t. that nuclear coordinate.

NONLinear

Specifies non-linear variable substitutions to be used in the definition of potential surfaces.

POLYnomial

Gives the different terms to be included in the fit of the polynomial to the energy data.

DATA

Potential energy surface data.

4.2.38.3.2. Input example

&MULA

Title
 Water molecule

Atoms
 O1
 H2
 H3
End Atoms

Internal Coordinates
 Bond  O1 H2
 Bond  O1 H3
 Angle H3 O1 H2
End Internal Coordinates

MxLevels
  0  3

Energies
 First
  0.0 eV
 Second
  3.78 eV

Geometry
 Cartesian
 First
  O1     0.0000000000      0.0000000000     -0.5000000000
  H2     1.6000000000      0.0000000000      1.1000000000
  H3    -1.6000000000      0.0000000000      1.1000000000
 End
 Second
  O1     0.0000000000      0.0000000000     -0.4500000000
  H2     1.7000000000      0.0000000000      1.0000000000
  H3    -1.7000000000      0.0000000000      1.0000000000
 End

ForceField
 First state
 Internal
  0.55 0.07 0.01
  0.07 0.55 0.01
  0.01 0.01 0.35
 Second state
 Internal
  0.50 0.03 0.01
  0.03 0.50 0.01
  0.01 0.01 0.25

DIPOles
  0.20 0.20 1.20

BroadPlot
LifeTime
 10.0E-15

NANO
PlotWindow
 260 305

End of input
&MULA

TITLe
 Benzene

ATOMs
  C1
  C2
  C3
  C4
  C5
  C6
  H1
  H2
  H3
  H4
  H5
  H6
End of Atoms

GEOMetry
 file

INTERNAL COORDINATES
 Bond    C1 C3
 Bond    C3 C5
 Bond    C5 C2
 Bond    C2 C6
 Bond    C6 C4
 Bond    C1 H1
 Bond    C2 H2
 Bond    C3 H3
 Bond    C4 H4
 Bond    C5 H5
 Bond    C6 H6
 Angle   C1 C3 C5
 Angle   C3 C5 C2
 Angle   C5 C2 C6
 Angle   C2 C6 C4
 Angle   H1 C1 C4
 Angle   H2 C2 C5
 Angle   H3 C3 C1
 Angle   H4 C4 C6
 Angle   H5 C5 C3
 Angle   H6 C6 C2
 Torsion C1 C3 C5 C2
 Torsion C3 C5 C2 C6
 Torsion C5 C2 C6 C4
 Torsion H1 C1 C4 C6
 Torsion H2 C2 C5 C3
 Torsion H3 C3 C1 C4
 Torsion H4 C4 C6 C2
 Torsion H5 C5 C3 C1
 Torsion H6 C6 C2 C5
END INTERNAL COORDINATES

VIBPLOT
 cyclic 4 1

ENERGIES
 First
  0.0 eV
 Second
  4.51 eV

MODES
 14 30 5 6 26 27 22 23 16 17 1 2 9 10
END

MXLE - MAXIMUM LEVEL of excitation (ground state - excited state)
  2 2

MXOR - MAXIMUM ORDER in transition dipole.
  1

OscStr

Transitions
 First
  0
 Second
  0 1 2

FORCEFIELD
 First
   file
 Second
   file

DIPOLES
 file