Carlier Group Gaussian User Manual - Virginia Tech

Carlier Group Gaussian User Manual 47
geometry and the force constants (note RCFC option in route section). Similarly, the
forward IRC input file was constructed in the same way:
%mem=4GB
%scr=h0461
%rwf=h0461
%int=h0461
%d2e=h0461
%nosave
%chk=h0461
#b3lyp/6-31G(d) irc=(RCFC,forward,maxpoints=20,stepsize=10)
geom=checkpoint
IRC calc based on h0441 MeBr alkylation TS of concave enolate
(simplified). geom from checkpoint
-1 1
Note that a priori one does not know which "way" a "forward" IRC calculation will
proceed from the transition structure. However, in this case, the "forward" IRC
calculation did go to the intended products.
In my experience the most critical factor for success in IRC calculations is setting the
step size. You have to play with this. If the step size is too big, I have seen at least two
unwanted things happen
1) you won't seem to progress along the reaction coordinate—this is confusing, because
you will think you need to further increase the step size—which is tragically deceptive.
2) when you further increase the step size, crazy stuff starts happening.
For example, in the present case with a stepsize of 10, this IRC runs smoothly in the
forward and reverse directions. With a stepsize of 50, this IRC runs only in the forward
direction and the first point is UP in energy from the transition structure. It will not go
anywhere productive in the backward direction with this large stepsize, even if the
phase is specified (bond axis for movement). With a step size of 25, it runs in the
forward direction, but again the energy of the first step is UP (not as much as when it
was 50). In both the cases of 50 and 25, the forward IRC gets close to the product, but
a vibrating behavior is seen and a stationary point is never reached. An attempt at
running the backward IRC with a step size of 100 leads to a vibration, and an explosion.
However, in the case of stepsize of 10, the forward and backward IRC go smoothly 20
points towards the product and SM respectively, but never give the message "Minimum
found." Nevertheless, both give a successful termination message.
Thus although you may be successful at getting the IRC calclulations to proceed
towards reactant and product, you may still not be successful at reaching your final
destinations ("Minimum found"). Do not dismay. You must first assess how much
progress you have made energetically, and to do this the easiest procedure is to take
your points of furthest progress, save these geometries, and initiate geometry