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Your List is a list of solutions with respect to a,b. If you want just one solution you can re-define it as

List=solve([eqn1,eqn2],a,b)


and then proceed as in your code; or if you want to get Poly as a list of polynomials (one for each solution), you can define it as

Poly=[ List[0]*fcn1+List[1]*fcn2 for List in solve([eqn1,eqn2],a,b) ]


Your List is a list of solutions with respect to a,b. If you want just one solution you can re-define it as

List=solve([eqn1,eqn2],a,b)
List=solve([eqn1,eqn2],a,b)[0]


and then proceed as in your code; or if you want to get Poly as a list of polynomials (one for each solution), you can define it as

Poly=[ List[0]*fcn1+List[1]*fcn2 for List in solve([eqn1,eqn2],a,b) ]