11.10 Harmonic Vibrational Analysis

11.10.2 Isotopic Substitutions

By default Q-Chem calculates vibrational frequencies using the atomic masses of the most abundant isotopes (taken from the Handbook of Chemistry and Physics, 63rd Edition). Masses of other isotopes can be specified using the $isotopes section and by setting the ISOTOPES $rem variable to TRUE. The format of the $isotopes section is as follows:

$isotopes
   number_of_isotope_loops  tp_flag
   number_of_atoms  [temp pressure] (loop 1)
   atom_number1   mass1
   atom_number2   mass2
   ...
   number_of_atoms  [temp pressure] (loop 2)
   atom_number1   mass1
   atom_number2   mass2
   ...
$end

Note:  Only the atoms whose masses are to be changed from the default values need to be specified. After each loop all masses are reset to the default values. Atoms are numbered according to the order in the $molecule section.

An initial loop using the default masses is always performed first. Subsequent loops use the user-specified atomic masses. Only those atoms whose masses are to be changed need to be included in the list, all other atoms will adopt the default masses. The output gives a full frequency analysis for each loop. Note that the calculation of vibrational frequencies in the additional loops only involves a rescaling of the computed Hessian, and therefore takes little additional computational time.

The first line of the $isotopes section specifies the number of substitution loops and also whether the temperature and pressure should be modified. The tp_flag setting should be set to 0 if the default temperature and pressure are to be used (298.18 K and 1 atm respectively), or else to 1 if they are to be altered. Note that the temperatures should be specified in Kelvin and pressures in atmospheres.

ISOTOPES
       Specifies if non-default masses are to be used in the frequency calculation.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       FALSE Use default masses only. TRUE Read isotope masses from $isotopes section.
RECOMMENDATION:
       None

Example 11.15  An EDF1/6-31+G* optimization, followed by a vibrational analysis. Doing the vibrational analysis at a stationary point is necessary for the results to be valid.

$molecule
   0  1
   C   1.08900   0.00000   0.00000
   C  -1.08900   0.00000   0.00000
   H   2.08900   0.00000   0.00000
   H  -2.08900   0.00000   0.00000
$end

$rem
   BASIS    3-21G
   JOBTYPE  opt
   METHOD   hf
$end

@@@

$molecule
   read
$end

$rem
   BASIS       3-21G
   JOBTYPE     freq
   METHOD      hf
   SCF_GUESS   read
   ISOTOPES    1
$end

$isotopes
   2   0           ! two loops, both at std temp and pressure
   4
     1   13.00336  ! All atoms are given non-default masses
     2   13.00336
     3   2.01410
     4   2.01410
   2
     3   2.01410   ! H’s replaced with D’s
     4   2.01410
$end