P_a = P.subs(dict(zip(a, val_a))) 

returns 

(0.450033195586719*x + 0.829322314411828)/(x**3*b[2, 0] + x**2*b[1, 0] + x*b
[0, 0] + 1)

You need to substitute individual MatrixElement objects like a[0], not the 
MatrixSymbol itself (which isn't even present in the expression P). 


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