HCN: transition state search with the CINEB method
Sample directory: adf/HCN_CINEB/
This example demonstrates the use of the Nudged Elastic Band method in ADF for finding a transition state of the HCN isomerisation reaction. A shell script used to run the example calculation is shown below:
$ADFBIN/adf <<eor
TITLE Test of the CI-NEB method
SYMMETRY C(S)
NOPRINT SCF SFO
UNITS
length Angstrom
angle Degree
END
ATOMS
1.C 0.000000 0.000000 0.000000
2.N XN 0.000000 0.000000
3.H XH YH 0.000000
END
GEOVAR
XN 1.180 1.163
XH 2.196 1.831 1.006 0.105 -0.718 -1.078
YH 0.000 0.799 1.122 1.163 0.813 0.000
END
BASIS
END
GEOMETRY
CINEB 9
iterations 150
OPTIM selected
converge grad=0.001
nebspring 1 0.06
END
integration 4.0
SCF
Convergence 0.00000001
END
eor
A few important points to note:
- Symmetry is set to Cs explicitly because all images must have the same symmetry but symmetry of the reaction products is higher, C∞. Thus, it is necessary to lower the overall symmetry to match the lowest.
- In the GEOVAR section, there are six values specified for the coordinates of the hydrogen atom. Thisi is necessary in order to bring the initial guess for the reaction path closer to the final result. Moreover, if only two values for YH were specified (0.0 and 0.0) then the hydrogen atom would be "dragged" along the C-N bond leading to unrealistic geometries and, eventually, to a failure.
- In the GEOMETRY section of the input, the number of NEB images is set to 9; the convergence criterion is lowered to 0.001; optimization of only the coordinates specified in the GEOVAR block is requested;
- the NEB spring parameter is set to a constant (energy-independent) value of 0.06 a.u.. The choice of the parameter depends on the stiffness of the bonds involved in the reaction and the value of the parameter should, in principle, be of about the same magnitude as the Hessian eigenvalue for the coordinates participating in the reaction.
