MATHEMATICAL

PART

HOW TO SOLVE
COMPLETE BASIS SET???
BASIS SET EXTRAPOLATION
METHOD
COMPLETE BASIS SET LIMIT
EXTRAPOLATION METHOD---
CONCEPT
COMPLETE BASIS SET LIMIT IS NOT A BASIS SET INSTEAD IT IS AN
EXTRAPOLATED ESTIMATE OF A RESULT OBTAINED USING A INFINITE
LARGE BASIS SET.
THE EXTRAPOLATION IS BASED ON MINIMUM OF 3 SEPARATE
CALCULATIONS WITH INCREASINGLY LARGE BASIS SET.
THE PROCEDURE IS AS FOLLOWS:: A GIVEN PROPERTY Y OF
INTEREST {E.G RELATIVE ENERGY, FREQUENCY,BOND LENGTH}
TWO MOST POPULAR EQUATIONS ARE AS FOLLOWS

Y(X)=YCBS + Ae-x
x=cardinal number of basis set, x=2 for DZ, x=3 for TZ
THERE ARE TWO SCHEMES FOR
EXTRAPOLATION
1.} Exponential function extrapolation
2.} Power function extrapolation scheme

WHY EXPONENTIAL EXTRAPOLATION????

ENERGETIC QUANTITIES TEND TO CONVERGE EXPONENTIALLY
BUT SUCH A BEHAVIOUR DECREASE AS THE QUANTITIES
BECOME LESS RELATED TO ENERGY.
SO EXPONENTIAL EXTRAPOLATION SCHEME IS MUCH MORE
ACCURATE.
 Exponential extrapolation
scheme::

Where E(X) = energy at incomplete basis set

E
= energy at complete basis set

& are constants

X is the cardinal number

X=2 for DZ

X=3 for TZ
In order to calculate E , & we need at least three equation..

Here X=2 for double zeta basis set

X=3 for triple zeta basis set
X=4 for quadruple zeta basis set
After solving these equations we get value of E (i.e
value of complete basis set)..
After solving these equations we also get
value for & ..
 AND,

WHERE
HOW TO SOLVE??????

We have two equations..